Xylose utilizing zymomonas mobilis with improved ethanol production in biomass hydrolysate medium

DOEpatents

Caimi, Perry G; Hitz, William D; Stieglitz, Barry; Viitanen, Paul V

2013-07-02

Xylose-utilizing, ethanol producing strains of Zymomonas mobilis with improved performance in medium comprising biomass hydrolysate were isolated using an adaptation process. Independently isolated strains were found to have independent mutations in the same coding region. Mutation in this coding may be engineered to confer the improved phenotype.

Fermentation of Soybean Meal Hydrolyzates with Saccharomyces cerevisiae and Zymomonas mobilis for Ethanol Production.

PubMed

Luján-Rhenals, Deivis E; Morawicki, Rubén O; Gbur, Edward E; Ricke, Steven C

2015-07-01

Most of the ethanol currently produced by fermentation is derived from sugar cane, corn, or beets. However, it makes good ecological and economic sense to use the carbohydrates contained in by-products and coproducts of the food processing industry for ethanol production. Soybean meal, a co-product of the production of soybean oil, has a relatively high carbohydrate content that could be a reasonable substrate for ethanol production after fermentable sugars are released via hydrolysis. In this research, the capability of Saccharomyces cerevisiae NRRL Y-2233 and Zymomonas mobilis subsp. mobilis NRRL B-4286 to produce ethanol was evaluated using soybean meal hydrolyzates as substrates for the fermentation. These substrates were produced from the dilute-acid hydrolysis of soybean meal at 135 °C for 45 min with 0, 0.5%, 1.25%, and 2% H2 SO4 and at 120 °C for 30 min with 1.25% H2 SO4 . Kinetic parameters of the fermentation were estimated using the logistic model. Ethanol production using S. cerevisiae was highest with the substrates obtained at 135 °C, 45 min, and 0.5% H2 SO4 and fermented for 8 h, 8 g/L (4 g ethanol/100 g fresh SBM), while Z. mobilis reached its maximum ethanol production, 9.2 g/L (4.6 g ethanol/100 g fresh SBM) in the first 20 h of fermentation with the same hydrolyzate. © 2015 Institute of Food Technologists®

Flocculating Zymomonas mobilis is a promising host to be engineered for fuel ethanol production from lignocellulosic biomass.

PubMed

Zhao, Ning; Bai, Yun; Liu, Chen-Guang; Zhao, Xin-Qing; Xu, Jian-Feng; Bai, Feng-Wu

2014-03-01

Whereas Saccharomyces cerevisiae uses the Embden-Meyerhof-Parnas pathway to metabolize glucose, Zymomonas mobilis uses the Entner-Doudoroff (ED) pathway. Employing the ED pathway, 50% less ATP is produced, which could lead to less biomass being accumulated during fermentation and an improved yield of ethanol. Moreover, Z. mobilis cells, which have a high specific surface area, consume glucose faster than S. cerevisiae, which could improve ethanol productivity. We performed ethanol fermentations using these two species under comparable conditions to validate these speculations. Increases of 3.5 and 3.3% in ethanol yield, and 58.1 and 77.8% in ethanol productivity, were observed in ethanol fermentations using Z. mobilis ZM4 in media containing ∼100 and 200 g/L glucose, respectively. Furthermore, ethanol fermentation bythe flocculating Z. mobilis ZM401 was explored. Although no significant difference was observed in ethanol yield and productivity, the flocculation of the bacterial species enabled biomass recovery by cost-effective sedimentation, instead of centrifugation with intensive capital investment and energy consumption. In addition, tolerance to inhibitory byproducts released during biomass pretreatment, particularly acetic acid and vanillin, was improved. These experimental results indicate that Z. mobilis, particularly its flocculating strain, is superior to S. cerevisiae as a host to be engineered for fuel ethanol production from lignocellulosic biomass. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Method of inactivation of an end product of energy metabolism in Zymomonas mobilis

DOEpatents

Zhang, Min [Lakewood, CO; Chou, Yat-Chen [Lakewood, CO

2008-05-20

The present invention briefly provides a method of site-specific insertion in Zymomonas, comprising, providing a Zymomonas gene fragment, interrupting a DNA sequence the fragment, and transforming the Zymomonas through homologous recombination with the interrupted fragment.

Pre-treatment step with Leuconostoc mesenteroides or L. pseudomesenteroides strains removes furfural from Zymomonas mobilis ethanolic fermentation broth

USDA-ARS?s Scientific Manuscript database

Furfural (furan-2-carboxaldehyde), formed during dilute acid hydrolysis of biomass, is an inhibitor of growth and ethanol production by Zymomonas mobilis. The present study used a biological pre-treatment to reduce that amount of furfural in a model biofuel fermentation broth. The pre-treatment in...

Improving furfural tolerance of Zymomonas mobilis by rewiring a sigma factor RpoD protein.

PubMed

Tan, Fu-Rong; Dai, Li-Chun; Wu, Bo; Qin, Han; Shui, Zong-Xia; Wang, Jing-Li; Zhu, Qi-Li; Hu, Qi-Chun; Ruan, Zhi-Yong; He, Ming-Xiong

2015-06-01

Furfural from lignocellulosic hydrolysates is the key inhibitor for bio-ethanol fermentation. In this study, we report a strategy of improving the furfural tolerance in Zymomonas mobilis on the transcriptional level by engineering its global transcription sigma factor (σ(70), RpoD) protein. Three furfural tolerance RpoD mutants (ZM4-MF1, ZM4-MF2, and ZM4-MF3) were identified from error-prone PCR libraries. The best furfural-tolerance strain ZM4-MF2 reached to the maximal cell density (OD600) about 2.0 after approximately 30 h, while control strain ZM4-rpoD reached its highest cell density of about 1.3 under the same conditions. ZM4-MF2 also consumed glucose faster and yield higher ethanol; expression levels and key Entner-Doudoroff (ED) pathway enzymatic activities were also compared to control strain under furfural stress condition. Our results suggest that global transcription machinery engineering could potentially be used to improve stress tolerance and ethanol production in Z. mobilis.

Identification of yeast and bacteria involved in the mezcal fermentation of Agave salmiana.

PubMed

Escalante-Minakata, P; Blaschek, H P; Barba de la Rosa, A P; Santos, L; De León-Rodríguez, A

2008-06-01

To identify the yeast and bacteria present in the mezcal fermentation from Agave salmiana. The restriction and sequence analysis of the amplified region, between 18S and 28S rDNA and 16S rDNA genes, were used for the identification of yeast and bacteria, respectively. Eleven different micro-organisms were identified in the mezcal fermentation. Three of them were the following yeast: Clavispora lusitaniae, Pichia fermentans and Kluyveromyces marxianus. The bacteria found were Zymomonas mobilis subsp. mobilis and Zymomonas mobilis subsp. pomaceae, Weissella cibaria, Weissella paramesenteroides, Lactobacillus pontis, Lactobacillus kefiri, Lactobacillus plantarum and Lactobacillus farraginis. The phylogenetic analysis of 16S rDNA and ITS sequences showed that microbial diversity present in mezcal is dominated by bacteria, mainly lactic acid bacteria species and Zymomonas mobilis. Pichia fermentans and K. marxianus could be micro-organisms with high potential for the production of some volatile compounds in mezcal. We identified the community of bacteria and yeast present in mezcal fermentation from Agave salmiana.

Transcriptome analysis of Zymomonas mobilis ZM4 reveals mechanisms of tolerance and detoxification of phenolic aldehyde inhibitors from lignocellulose pretreatment

USDA-ARS?s Scientific Manuscript database

Background: Phenolic aldehydes generated from lignocellulose pretreatment exhibited severe toxic inhibitions on microbial growth and fermentation. Numerous tolerance studies against furfural, 5-hydroxymethyl-2-furaldehyde (HMF), acetate, and ethanol were reported, but studies on inhibition of phenol...

Improvement of ethanol productivity and energy efficiency by degradation of inhibitors using recombinant Zymomonas mobilis (pHW20a-fdh).

PubMed

Dong, Hong-Wei; Fan, Li-Qiang; Luo, Zichen; Zhong, Jian-Jiang; Ryu, Dewey D Y; Bao, Jie

2013-09-01

Toxic compounds, such as formic acid, furfural, and hydroxymethylfurfural (HMF) generated during pretreatment of corn stover (CS) at high temperature and low pH, inhibit growth of Zymomonas mobilis and lower the conversion efficiency of CS to biofuel and other products. The inhibition of toxic compounds is considered as one of the major technical barriers in the lignocellulose bioconversion. In order to detoxify and/or degrade these toxic compounds by the model ethanologenic strain Z. mobilis itself in situ the fermentation medium, we constructed a recombinant Z. mobilis ZM4 (pHW20a-fdh) strain that is capable of degrading toxic inhibitor, formate. This is accomplished by cloning heterologous formate dehydrogenase gene (fdh) from Saccharomyces cerevisiae and by coupling this reaction of NADH regeneration reaction system with furfural and HMF degradation in the recombinant Z. mobilis strain. The NADH regeneration reaction also improved both the energy efficiency and cell physiological activity of the recombinant organism, which were definitely confirmed by the improved cell growth, ethanol yield, and ethanol productivity during fermentation with CS hydrolysate. Copyright © 2013 Wiley Periodicals, Inc.

Development of corn silk as a biocarrier for Zymomonas mobilis biofilms in ethanol production from rice straw.

PubMed

Todhanakasem, Tatsaporn; Tiwari, Rashmi; Thanonkeo, Pornthap

2016-01-01

Z. mobilis cell immobilization has been proposed as an effective means of improving ethanol production. In this work, polystyrene and corn silk were used as biofilm developmental matrices for Z. mobilis ethanol production with rice straw hydrolysate as a substrate. Rice straw was hydrolyzed by dilute sulfuric acid (H2SO4) and enzymatic hydrolysis. The final hydrolysate contained furfural (271.95 ± 76.30 ppm), 5-hydroxymethyl furfural (0.07 ± 0.00 ppm), vanillin (1.81 ± 0.00 ppm), syringaldehyde (5.07 ± 0.83 ppm), 4-hydroxybenzaldehyde (4-HB) (2.39 ± 1.20 ppm) and acetic acid (0.26 ± 0.08%). Bacterial attachment or biofilm formation of Z. mobilis strain TISTR 551 on polystyrene and delignified corn silk carrier provided significant ethanol yields. Results showed up to 0.40 ± 0.15 g ethanol produced/g glucose consumed when Z. mobilis was immobilized on a polystyrene carrier and 0.51 ± 0.13 g ethanol produced/g glucose consumed when immobilized on delignified corn silk carrier under batch fermentation by Z. mobilis TISTR 551 biofilm. The higher ethanol yield from immobilized, rather than free living, Z. mobilis could possibly be explained by a higher cell density, better control of anaerobic conditions and higher toxic tolerance of Z. mobilis biofilms over free cells.

Inhibition of growth of Zymomonas mobilis by model compounds found in lignocellulosic hydrolysates

PubMed Central

2013-01-01

Background During the pretreatment of biomass feedstocks and subsequent conditioning prior to saccharification, many toxic compounds are produced or introduced which inhibit microbial growth and in many cases, production of ethanol. An understanding of the toxic effects of compounds found in hydrolysate is critical to improving sugar utilization and ethanol yields in the fermentation process. In this study, we established a useful tool for surveying hydrolysate toxicity by measuring growth rates in the presence of toxic compounds, and examined the effects of selected model inhibitors of aldehydes, organic and inorganic acids (along with various cations), and alcohols on growth of Zymomonas mobilis 8b (a ZM4 derivative) using glucose or xylose as the carbon source. Results Toxicity strongly correlated to hydrophobicity in Z. mobilis, which has been observed in Escherichia coli and Saccharomyces cerevisiae for aldehydes and with some exceptions, organic acids. We observed Z. mobilis 8b to be more tolerant to organic acids than previously reported, although the carbon source and growth conditions play a role in tolerance. Growth in xylose was profoundly inhibited by monocarboxylic organic acids compared to growth in glucose, whereas dicarboxylic acids demonstrated little or no effects on growth rate in either substrate. Furthermore, cations can be ranked in order of their toxicity, Ca++ > > Na+ > NH4+ > K+. HMF (5-hydroxymethylfurfural), furfural and acetate, which were observed to contribute to inhibition of Z. mobilis growth in dilute acid pretreated corn stover hydrolysate, do not interact in a synergistic manner in combination. We provide further evidence that Z. mobilis 8b is capable of converting the aldehydes furfural, vanillin, 4-hydroxybenzaldehyde and to some extent syringaldehyde to their alcohol forms (furfuryl, vanillyl, 4-hydroxybenzyl and syringyl alcohol) during fermentation. Conclusions Several key findings in this report provide a mechanism for predicting toxic contributions of inhibitory components of hydrolysate and provide guidance for potential process development, along with potential future strain improvement and tolerance strategies. PMID:23837621

Genetic improvement of Escherichia coli for ethanol production: Chromosomal integration of Zymomonas mobilis genes encoding pyruvate decarboxylase and alcohol dehydrogenase II

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ohta, Kazuyoshi; Beall, D.S.; Mejia, J.P.

1991-04-01

Zymomonas mobilis genes for pyruvate decarboxylase (pdc) and alcohol dehydrogenase II (adhB) were integrated into the Escherichia coli chromosome within or near the pyruvate formate-lyase gene (pfl). Integration improved the stability of the Z. mobilis genes in E. coli, but further selection was required to increase expression. Spontaneous mutants were selected for resistance to high levels of chloramphenicol that also expressed high levels of the Z. mobilis genes. Analogous mutants were selected for increased expression of alcohol dehydrogenase on aldehyde indicator plates. These mutants were functionally equivalent to the previous plasmid-based strains for the fermentation of xylose and glucose tomore » ethanol. Ethanol concentrations of 54.4 and 41.6 g/liter were obtained from 10% glucose and 8% xylose, respectively. The efficiency of conversion exceeded theoretical limits (0.51 g of ethanol/g of sugar) on the basis of added sugars because of the additional production of ethanol from the catabolism of complex nutrients. Further mutations were introduced to inactivate succinate production (frd) and to block homologous recombination (recA).« less

Systems Biology Analysis of Zymomonas mobilis ZM4 Ethanol Stress Responses

PubMed Central

Yang, Shihui; Pan, Chongle; Tschaplinski, Timothy J.; Hurst, Gregory B.; Engle, Nancy L.; Zhou, Wen; Dam, PhuongAn; Xu, Ying; Rodriguez, Miguel; Dice, Lezlee; Johnson, Courtney M.; Davison, Brian H.; Brown, Steven D.

2013-01-01

Background Zymomonas mobilis ZM4 is a capable ethanologenic bacterium with high ethanol productivity and ethanol tolerance. Previous studies indicated that several stress-related proteins and changes in the ZM4 membrane lipid composition may contribute to ethanol tolerance. However, the molecular mechanisms of its ethanol stress response have not been elucidated fully. Methodology/Principal Findings In this study, ethanol stress responses were investigated using systems biology approaches. Medium supplementation with an initial 47 g/L (6% v/v) ethanol reduced Z. mobilis ZM4 glucose consumption, growth rate and ethanol productivity compared to that of untreated controls. A proteomic analysis of early exponential growth identified about one thousand proteins, or approximately 55% of the predicted ZM4 proteome. Proteins related to metabolism and stress response such as chaperones and key regulators were more abundant in the early ethanol stress condition. Transcriptomic studies indicated that the response of ZM4 to ethanol is dynamic, complex and involves many genes from all the different functional categories. Most down-regulated genes were related to translation and ribosome biogenesis, while the ethanol-upregulated genes were mostly related to cellular processes and metabolism. Transcriptomic data were used to update Z. mobilis ZM4 operon models. Furthermore, correlations among the transcriptomic, proteomic and metabolic data were examined. Among significantly expressed genes or proteins, we observe higher correlation coefficients when fold-change values are higher. Conclusions Our study has provided insights into the responses of Z. mobilis to ethanol stress through an integrated “omics” approach for the first time. This systems biology study elucidated key Z. mobilis ZM4 metabolites, genes and proteins that form the foundation of its distinctive physiology and its multifaceted response to ethanol stress. PMID:23874800

Transcriptome profiling of Zymomonas mobilis under furfural stress.

PubMed

He, Ming-xiong; Wu, Bo; Shui, Zong-xia; Hu, Qi-chun; Wang, Wen-guo; Tan, Fu-rong; Tang, Xiao-yu; Zhu, Qi-li; Pan, Ke; Li, Qing; Su, Xiao-hong

2012-07-01

Furfural from lignocellulosic hydrolysates is the prevalent inhibitor to microorganisms during cellulosic ethanol production, but the molecular mechanisms of tolerance to this inhibitor in Zymomonas mobilis are still unclear. In this study, genome-wide transcriptional responses to furfural were investigated in Z. mobilis using microarray analysis. We found that 433 genes were differentially expressed in response to furfural. Furfural up- or down-regulated genes related to cell wall/membrane biogenesis, metabolism, and transcription. However, furfural has a subtle negative effect on Entner-Doudoroff pathway mRNAs. Our results revealed that furfural had effects on multiple aspects of cellular metabolism at the transcriptional level and that membrane might play important roles in response to furfural. This research has provided insights into the molecular response to furfural in Z. mobilis, and it will be helpful to construct more furfural-resistant strains for cellulosic ethanol production.

Cloning, sequencing, and expression of the Zymomonas mobilis phosphoglycerate mutase gene (pgm) in Escherichia coli.

PubMed Central

Yomano, L P; Scopes, R K; Ingram, L O

1993-01-01

Phosphoglycerate mutase is an essential glycolytic enzyme for Zymomonas mobilis, catalyzing the reversible interconversion of 3-phosphoglycerate and 2-phosphoglycerate. The pgm gene encoding this enzyme was cloned on a 5.2-kbp DNA fragment and expressed in Escherichia coli. Recombinants were identified by using antibodies directed against purified Z. mobilis phosphoglycerate mutase. The pgm gene contains a canonical ribosome-binding site, a biased pattern of codon usage, a long upstream untranslated region, and four promoters which share sequence homology. Interestingly, adhA and a D-specific 2-hydroxyacid dehydrogenase were found on the same DNA fragment and appear to form a cluster of genes which function in central metabolism. The translated sequence for Z. mobilis pgm was in full agreement with the 40 N-terminal amino acid residues determined by protein sequencing. The primary structure of the translated sequence is highly conserved (52 to 60% identity with other phosphoglycerate mutases) and also shares extensive homology with bisphosphoglycerate mutases (51 to 59% identity). Since Southern blots indicated the presence of only a single copy of pgm in the Z. mobilis chromosome, it is likely that the cloned pgm gene functions to provide both activities. Z. mobilis phosphoglycerate mutase is unusual in that it lacks the flexible tail and lysines at the carboxy terminus which are present in the enzyme isolated from all other organisms examined. Images PMID:8320209

N 2 gas is an effective fertilizer for bioethanol production by Zymomonas mobilis

DOE PAGES

Kremer, Timothy A.; LaSarre, Breah; Posto, Amanda L.; ...

2015-02-02

A nascent cellulosic ethanol industry is struggling to become cost-competitive against corn ethanol and gasoline. Millions of dollars are spent on nitrogen supplements to make up for the low nitrogen content of the cellulosic feedstock. In this paper, we show for the first time to our knowledge that the ethanol-producing bacterium, Zymomonas mobilis, can use N 2 gas in lieu of traditional nitrogen supplements. Despite being an electron-intensive process, N 2 fixation by Z. mobilis did not divert electrons away from ethanol production, as the ethanol yield was greater than 97% of the theoretical maximum. In a defined medium, Z.more » mobilis produced ethanol 50% faster per cell and generated half the unwanted biomass when supplied N 2 instead of ammonium. In a cellulosic feedstock-derived medium, Z. mobilis achieved a similar cell density and a slightly higher ethanol yield when supplied N 2 instead of the industrial nitrogen supplement, corn steep liquor. Finally, we estimate that N 2-utilizing Z. mobilis could save a cellulosic ethanol production facility more than $1 million/y.« less

Zymomonas mobilis: a novel platform for future biorefineries.

PubMed

He, Ming Xiong; Wu, Bo; Qin, Han; Ruan, Zhi Yong; Tan, Fu Rong; Wang, Jing Li; Shui, Zong Xia; Dai, Li Chun; Zhu, Qi Li; Pan, Ke; Tang, Xiao Yu; Wang, Wen Guo; Hu, Qi Chun

2014-01-01

Biosynthesis of liquid fuels and biomass-based building block chemicals from microorganisms have been regarded as a competitive alternative route to traditional. Zymomonas mobilis possesses a number of desirable characteristics for its special Entner-Doudoroff pathway, which makes it an ideal platform for both metabolic engineering and commercial-scale production of desirable bio-products as the same as Escherichia coli and Saccharomyces cerevisiae based on consideration of future biomass biorefinery. Z. mobilis has been studied extensively on both fundamental and applied level, which will provide a basis for industrial biotechnology in the future. Furthermore, metabolic engineering of Z. mobilis for enhancing bio-ethanol production from biomass resources has been significantly promoted by different methods (i.e. mutagenesis, adaptive laboratory evolution, specific gene knock-out, and metabolic engineering). In addition, the feasibility of representative metabolites, i.e. sorbitol, bionic acid, levan, succinic acid, isobutanol, and isobutanol produced by Z. mobilis and the strategies for strain improvements are also discussed or highlighted in this paper. Moreover, this review will present some guidelines for future developments in the bio-based chemical production using Z. mobilis as a novel industrial platform for future biofineries.

N2 gas is an effective fertilizer for bioethanol production by Zymomonas mobilis

PubMed Central

Kremer, Timothy A.; LaSarre, Breah; Posto, Amanda L.; McKinlay, James B.

2015-01-01

A nascent cellulosic ethanol industry is struggling to become cost-competitive against corn ethanol and gasoline. Millions of dollars are spent on nitrogen supplements to make up for the low nitrogen content of the cellulosic feedstock. Here we show for the first time to our knowledge that the ethanol-producing bacterium, Zymomonas mobilis, can use N2 gas in lieu of traditional nitrogen supplements. Despite being an electron-intensive process, N2 fixation by Z. mobilis did not divert electrons away from ethanol production, as the ethanol yield was greater than 97% of the theoretical maximum. In a defined medium, Z. mobilis produced ethanol 50% faster per cell and generated half the unwanted biomass when supplied N2 instead of ammonium. In a cellulosic feedstock-derived medium, Z. mobilis achieved a similar cell density and a slightly higher ethanol yield when supplied N2 instead of the industrial nitrogen supplement, corn steep liquor. We estimate that N2-utilizing Z. mobilis could save a cellulosic ethanol production facility more than $1 million/y. PMID:25646422

Pre-treatment step with Leuconostoc mesenteroides or L. pseudomesenteroides strains removes furfural from Zymomonas mobilis ethanolic fermentation broth.

PubMed

Hunter, William J; Manter, Daniel K

2014-10-01

Furfural is an inhibitor of growth and ethanol production by Zymomonas mobilis. This study used a naturally occurring (not GMO) biological pre-treatment to reduce that amount of furfural in a model fermentation broth. Pre-treatment involved inoculating and incubating the fermentation broth with strains of Leuconostoc mesenteroides or Leuconostoc pseudomesenteroides. The Leuconostoc strains converted furfural to furfuryl alcohol without consuming large amounts of dextrose in the process. Coupling this pre-treatment to ethanolic fermentation reduced furfural in the broth and improved growth, dextrose uptake and ethanol formation. Pre-treatment permitted ethanol formation in the presence of 5.2 g L(-1) furfural, which was otherwise inhibitive. The pre-treatment and presence of the Leuconostoc strains in the fermentation broth did not interfere with Z. mobilis ethanolic fermentation or the amounts of ethanol produced. The method suggests a possible technique for reducing the effect that furfural has on the production of ethanol for use as a biofuel. Published by Elsevier Ltd.

Evaluation and optimization of ethanol production from carob pod extract by Zymomonas mobilis using response surface methodology.

PubMed

Vaheed, Hossein; Shojaosadati, Seyed Abbas; Galip, Hasan

2011-01-01

In this research, ethanol production from carob pod extract (extract) using Zymomonas mobilis with medium optimized by Plackett-Burman (P-B) and response surface methodologies (RSM) was studied. Z. mobilis was recognized as useful for ethanol production from carob pod extract. The effects of initial concentrations of sugar, peptone, and yeast extract as well as agitation rate (rpm), pH, and culture time in nonhydrolyzed carob pod extract were investigated. Significantly affecting variables (P = 0.05) in the model obtained from RSM studies were: weights of bacterial inoculum, initial sugar, peptone, and yeast extract. Acid hydrolysis was useful to complete conversion of sugars to glucose and fructose. Nonhydrolyzed extract showed higher ethanol yield and residual sugar compared with hydrolyzed extract. Ethanol produced (g g(-1) initial sugar, as the response) was not significantly different (P = 0.05) when Z. mobilis performance was compared in hydrolyzed and nonhydrolyzed extract. The maximum ethanol of 0.34 ± 0.02 g g(-1) initial sugar was obtained at 30°C, initial pH 5.2, and 80 rpm, using concentrations (g per 50 mL culture media) of: inoculum bacterial dry weight, 0.017; initial sugar, 5.78; peptone, 0.43; yeast extract, 0.43; and culture time of 36 h.

Alkaline/peracetic acid as a pretreatment of lignocellulosic biomass for ethanol fuel production

NASA Astrophysics Data System (ADS)

Teixeira, Lincoln Cambraia

Peracetic acid is a lignin oxidation pretreatment with low energy input by which biomass can be treated in a silo type system for improving enzymatic digestibility of lignocellulosic materials for ethanol production. Experimentally, ground hybrid poplar wood and sugar cane bagasse are placed in plastic bags and a peracetic acid solution is added to the biomass in different concentrations based on oven-dry biomass. The ratio of solution to biomass is 6:1; after initial mixing of the resulting paste, a seven-day storage period at about 20°C is used in this study. As a complementary method, a series of pre-pretreatments using stoichiometric amounts of sodium hydroxide and ammonium hydroxide based on 4-methyl-glucuronic acid and acetyl content in the biomass is been performed before addition of peracetic acid. The alkaline solutions are added to the biomass in a ratio of 14:1 solution to biomass; the slurry is mixed for 24 hours at ambient temperature. The above procedures give high xylan content substrates. Consequently, xylanase/beta-glucosidase combinations are more effective than cellulase preparations in hydrolyzing these materials. The pretreatment effectiveness is evaluated using standard enzymatic hydrolysis and simultaneous saccharification and cofermentation (SSCF) procedures. Hybrid poplar wood pretreated with 15 and 21% peracetic acid based on oven-dry weight of wood gives glucan conversion yields of 76.5 and 98.3%, respectively. Sugar cane bagasse pretreated with the same loadings gives corresponding yields of 85.9 and 93.1%. Raw wood and raw bagasse give corresponding yields of 6.8 and 28.8%, respectively. The combined 6% NaOH/15% peracetic acid pretreatments increase the glucan conversion yields from 76.5 to 100.0% for hybrid poplar wood and from 85.9 to 97.6% for sugar cane bagasse. Respective ethanol yields of 92.8 and 91.9% are obtained from 6% NaOH/15% peracetic acid pretreated materials using recombinant Zymomonas mobilis CP4/pZB5. Peracetic acid pretreatment improves enzymatic digestibility of hybrid poplar wood and sugar cane bagasse. Based on reduction of acetyl groups in the two lignocellulosic materials, alkaline pre-pretreatments are helpful in reducing peracetic acid requirements in the pretreatment and consequently diminishing growth inhibition of the bacteria that was observed using higher peracetic acid loadings.

Detrimental effect of increasing sugar concentrations on ethanol production from maize or decorticated sorghum mashes fermented with Saccharomyces cerevisiae or Zymomonas mobilis: biofuels and environmental biotechnology.

PubMed

Pérez-Carrillo, Esther; Luisa Cortés-Callejas, M; Sabillón-Galeas, Luis E; Montalvo-Villarreal, Jorge L; Canizo, Jesica R; Georgina Moreno-Zepeda, M; Serna-Saldivar, Sergio O

2011-02-01

The efficiency of ethanol fermentation, as affected by grain source (maize and decorticated red sorghum), total sugar concentration (13 or 20° Plato) and type of microorganism (Saccharomyces cerevisiae or Zymomonas mobilis) was studied. Maize mashes yielded 0.32 l ethanol kg(-1) ground grain whereas mashes prepared with decorticated red sorghum produced 0.28 l ethanol kg(-1). Both microorganisms yielded similar amounts of ethanol. However, high-gravity mashes (20° Plato) yielded lower amounts of ethanol compared to counterparts adjusted to 13° Plato (0.28 vs. 0.22 l ethanol kg(-1) ground grains). In decorticated sorghum mashes adjusted to 20° P, Z. mobilis produced 40 ml kg(-1) more ethanol compared to S. cerevisiae. In addition, Z. mobilis had a lower dependency on nitrogenous compounds.

Continuous production of ethanol with Zymomonas mobilis growing on Jerusalem artichoke juice

DOE Office of Scientific and Technical Information (OSTI.GOV)

Allais, J.J.; Torres, E.F.; Baratti, J.

1987-04-01

Recent work from the authors laboratory has shown that, compared to yeasts, much higher ethanol productivity and yield can be obtained in batch or continuous cultures using the bacterium Zymomonas mobilis grown on fructose media. In batch culture, hydrolyzed Jerusalem artichoke juice with sugar concentrations ranging from 100 to 250 g/L can be converted efficiently to ethanol. The present work describes the conversion of the hydrolyzed juice to ethanol in continuous culture. The extraction and enzymatic hydrolysis of inulin from the tubers of Jerusalem artichoke is also reported.

High expression Zymomonas promoters

DOEpatents

Viitanen, Paul V [West Chester, PA; Tao, Luan [Havertown, PA; Zhang, Yuying [New Hope, PA; Caimi, Perry G [Kennett Square, PA; McCole, Laura : Zhang, Min; Chou, Yat-Chen [Lakewood, CO; McCutchen, Carol M [Wilmington, DE; Franden, Mary Ann [Centennial, CO

2011-08-02

Identified are mutants of the promoter of the Z. mobilis glyceraldehyde-3-phosphate dehydrogenase gene, which direct improved expression levels of operably linked heterologous nucleic acids. These are high expression promoters useful for expression of chimeric genes in Zymomonas, Zymobacter, and other related bacteria.

Zymomonas mobilis: a novel platform for future biorefineries

PubMed Central

2014-01-01

Biosynthesis of liquid fuels and biomass-based building block chemicals from microorganisms have been regarded as a competitive alternative route to traditional. Zymomonas mobilis possesses a number of desirable characteristics for its special Entner-Doudoroff pathway, which makes it an ideal platform for both metabolic engineering and commercial-scale production of desirable bio-products as the same as Escherichia coli and Saccharomyces cerevisiae based on consideration of future biomass biorefinery. Z. mobilis has been studied extensively on both fundamental and applied level, which will provide a basis for industrial biotechnology in the future. Furthermore, metabolic engineering of Z. mobilis for enhancing bio-ethanol production from biomass resources has been significantly promoted by different methods (i.e. mutagenesis, adaptive laboratory evolution, specific gene knock-out, and metabolic engineering). In addition, the feasibility of representative metabolites, i.e. sorbitol, bionic acid, levan, succinic acid, isobutanol, and isobutanol produced by Z. mobilis and the strategies for strain improvements are also discussed or highlighted in this paper. Moreover, this review will present some guidelines for future developments in the bio-based chemical production using Z. mobilis as a novel industrial platform for future biofineries. PMID:25024744

Can Zymomonas mobilis Substitute Saccharomyces cerevisiae in Cereal Dough Leavening?

PubMed Central

Musatti, Alida; Mapelli, Chiara

2018-01-01

Baker’s yeast intolerance is rising among Western populations, where Saccharomyces cerevisiae is spread in fermented food and food components. Zymomonas mobilis is a bacterium commonly used in tropical areas to produce alcoholic beverages, and it has only rarely been considered for dough leavening probably because it only ferments glucose, fructose and sucrose, which are scarcely present in flour. However, through alcoholic fermentation, similarly to S. cerevisiae, it provides an equimolar mixture of ethanol and CO2 that can rise a dough. Here, we propose Z. mobilis as a new leavening agent, as an alternative to S. cerevisiae, overcoming its technological limit with different strategies: (1) adding glucose to the dough formulation; and (2) exploiting the maltose hydrolytic activity of Lactobacillus sanfranciscensis associated with Z. mobilis. CO2 production, dough volume increase, pH value, microbial counts, sugars consumption and ethanol production were monitored. Results suggest that glucose addition to the dough lets Z. mobilis efficiently leaven a dough, while glucose released by L. sanfranciscensis is not so well fermented by Z. mobilis, probably due to the strong acidification. Nevertheless, the use of Z. mobilis as a leavening agent could contribute to increasing the variety of baked goods alternative to those leavened by S. cerevisiae. PMID:29659515

Purification, crystallization and X-ray crystallographic analysis of a putative exopolyphosphatase from Zymomonas mobilis

PubMed Central

Zhang, Aili; Guo, Erhong; Qian, Lanfang; Tang, Nga-Yeung; Watt, Rory M.; Bartlam, Mark

2016-01-01

Exopolyphosphatase (PPX) enzymes degrade inorganic polyphosphate (poly-P), which is essential for the survival of microbial cells in response to external stresses. In this study, a putative exopolyphosphatase from Zymomonas mobilis (ZmPPX) was crystallized. Crystals of the wild-type enzyme diffracted to 3.3 Å resolution and could not be optimized further. The truncation of 29 amino acids from the N-terminus resulted in crystals that diffracted to 1.8 Å resolution. The crystals belonged to space group C2, with unit-cell parameters a = 122.0, b = 47.1, c = 89.5 Å, α = γ = 90, β = 124.5°. An active-site mutant that crystallized in the same space group and with similar unit-cell parameters diffracted to 1.56 Å resolution. One molecule was identified per asymmetric unit. Analytical ultracentrifugation confirmed that ZmPPX forms a dimer in solution. It was confirmed that ZmPPX possesses exopolyphosphatase activity against a synthetic poly-P substrate. PMID:26919520

Purification, crystallization and X-ray crystallographic analysis of a putative exopolyphosphatase from Zymomonas mobilis.

PubMed

Zhang, Aili; Guo, Erhong; Qian, Lanfang; Tang, Nga-Yeung; Watt, Rory M; Bartlam, Mark

2016-03-01

Exopolyphosphatase (PPX) enzymes degrade inorganic polyphosphate (poly-P), which is essential for the survival of microbial cells in response to external stresses. In this study, a putative exopolyphosphatase from Zymomonas mobilis (ZmPPX) was crystallized. Crystals of the wild-type enzyme diffracted to 3.3 Å resolution and could not be optimized further. The truncation of 29 amino acids from the N-terminus resulted in crystals that diffracted to 1.8 Å resolution. The crystals belonged to space group C2, with unit-cell parameters a = 122.0, b = 47.1, c = 89.5 Å, α = γ = 90, β = 124.5°. An active-site mutant that crystallized in the same space group and with similar unit-cell parameters diffracted to 1.56 Å resolution. One molecule was identified per asymmetric unit. Analytical ultracentrifugation confirmed that ZmPPX forms a dimer in solution. It was confirmed that ZmPPX possesses exopolyphosphatase activity against a synthetic poly-P substrate.

Zymomonas with improved xylose utilization

DOEpatents

Viitanen, Paul V [West Chester, PA; Tao, Luan [Havertown, PA; Zhang, Yuying [New Hope, PA; Caimi, Perry G [Kennett Square, PA; McCutchen, Carol M [Wilmington, DE; McCole, Laura [East Fallowfield, PA; Zhang, Min [Lakewood, CO; Chou, Yat-Chen [Lakewood, CO; Franden, Mary Ann [Centennial, CO

2011-08-16

Strains of Zymomonas were engineered by introducing a chimeric xylose isomerase gene that contains a mutant promoter of the Z. mobilis glyceraldehyde-3-phosphate dehydrogenase gene. The promoter directs increased expression of xylose isomerase, and when the strain is in addition engineered for expression of xylulokinase, transaldolase and transketolase, improved utilization of xylose is obtained.

Ethanol production by Escherichia coli strains co-expressing Zymomonas PDC and ADH genes

DOEpatents

Ingram, Lonnie O.; Conway, Tyrrell; Alterthum, Flavio

1991-01-01

A novel operon and plasmids comprising genes which code for the alcohol dehydrogenase and pyruvate decarboxylase activities of Zymomonas mobilis are described. Also disclosed are methods for increasing the growth of microorganisms or eukaryotic cells and methods for reducing the accumulation of undesirable metabolic products in the growth medium of microorganisms or cells.

Genetic engineering and improvement of a Zymomonas mobilis for arabinose utilization and its performance on pretreated corn stover hydrolyzate

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chou, Yat -Chen; Linger, Jeffrey; Yang, Shihui

In this paper, a glucose, xylose and arabinose utilizing Zymomonas mobilis strain was constructed by incorporating arabinose catabolic pathway genes, araBAD encoding L-ribulokinase, L-arabinose isomerase and L-ribulose-5-phosphate- 4-epimerase in a glucose, xylose co-fermenting host, 8b, using a transposition integration approach. Further improvement on this arabinose-capable integrant, 33C was achieved by applying a second transposition to create a genomic knockout (KO) mutant library. Using arabinose as a sole carbon source and a selection pressure, the KO library was subjected to a growth-enrichment process involving continuous sub-culturing for over 120 generations. Strain 13-1-17, isolated from such process demonstrated significant improvement in metabolizingmore » arabinose in a dilute acid pretreated, saccharified corn stover slurry. Through Next Generation Sequencing (NGS) analysis, integration sites of the transposons were identified. Furthermore, multiple additional point mutations (SNPs: Single Nucleotide Polymorphisms) were discovered in 13-1-17, affecting genes araB and RpiB in the genome. Finally, we speculate that these mutations may have impacted the expression of the enzymes coded by these genes, ribulokinase and Ribose 5-P-isomerase, thus attributing to the improvement of the arabinose utilization.« less

Genetic engineering and improvement of a Zymomonas mobilis for arabinose utilization and its performance on pretreated corn stover hydrolyzate

DOE PAGES

Chou, Yat -Chen; Linger, Jeffrey; Yang, Shihui; ...

2015-04-28

In this paper, a glucose, xylose and arabinose utilizing Zymomonas mobilis strain was constructed by incorporating arabinose catabolic pathway genes, araBAD encoding L-ribulokinase, L-arabinose isomerase and L-ribulose-5-phosphate- 4-epimerase in a glucose, xylose co-fermenting host, 8b, using a transposition integration approach. Further improvement on this arabinose-capable integrant, 33C was achieved by applying a second transposition to create a genomic knockout (KO) mutant library. Using arabinose as a sole carbon source and a selection pressure, the KO library was subjected to a growth-enrichment process involving continuous sub-culturing for over 120 generations. Strain 13-1-17, isolated from such process demonstrated significant improvement in metabolizingmore » arabinose in a dilute acid pretreated, saccharified corn stover slurry. Through Next Generation Sequencing (NGS) analysis, integration sites of the transposons were identified. Furthermore, multiple additional point mutations (SNPs: Single Nucleotide Polymorphisms) were discovered in 13-1-17, affecting genes araB and RpiB in the genome. Finally, we speculate that these mutations may have impacted the expression of the enzymes coded by these genes, ribulokinase and Ribose 5-P-isomerase, thus attributing to the improvement of the arabinose utilization.« less

Complete genome sequence and the expression pattern of plasmids of the model ethanologen Zymomonas mobilis ZM4 and its xylose-utilizing derivatives 8b and 2032.

PubMed

Yang, Shihui; Vera, Jessica M; Grass, Jeff; Savvakis, Giannis; Moskvin, Oleg V; Yang, Yongfu; McIlwain, Sean J; Lyu, Yucai; Zinonos, Irene; Hebert, Alexander S; Coon, Joshua J; Bates, Donna M; Sato, Trey K; Brown, Steven D; Himmel, Michael E; Zhang, Min; Landick, Robert; Pappas, Katherine M; Zhang, Yaoping

2018-01-01

Zymomonas mobilis is a natural ethanologen being developed and deployed as an industrial biofuel producer. To date, eight Z. mobilis strains have been completely sequenced and found to contain 2-8 native plasmids. However, systematic verification of predicted Z. mobilis plasmid genes and their contribution to cell fitness has not been hitherto addressed. Moreover, the precise number and identities of plasmids in Z. mobilis model strain ZM4 have been unclear. The lack of functional information about plasmid genes in ZM4 impedes ongoing studies for this model biofuel-producing strain. In this study, we determined the complete chromosome and plasmid sequences of ZM4 and its engineered xylose-utilizing derivatives 2032 and 8b. Compared to previously published and revised ZM4 chromosome sequences, the ZM4 chromosome sequence reported here contains 65 nucleotide sequence variations as well as a 2400-bp insertion. Four plasmids were identified in all three strains, with 150 plasmid genes predicted in strain ZM4 and 2032, and 153 plasmid genes predicted in strain 8b due to the insertion of heterologous DNA for expanded substrate utilization. Plasmid genes were then annotated using Blast2GO, InterProScan, and systems biology data analyses, and most genes were found to have apparent orthologs in other organisms or identifiable conserved domains. To verify plasmid gene prediction, RNA-Seq was used to map transcripts and also compare relative gene expression under various growth conditions, including anaerobic and aerobic conditions, or growth in different concentrations of biomass hydrolysates. Overall, plasmid genes were more responsive to varying hydrolysate concentrations than to oxygen availability. Additionally, our results indicated that although all plasmids were present in low copy number (about 1-2 per cell), the copy number of some plasmids varied under specific growth conditions or due to heterologous gene insertion. The complete genome of ZM4 and two xylose-utilizing derivatives is reported in this study, with an emphasis on identifying and characterizing plasmid genes. Plasmid gene annotation, validation, expression levels at growth conditions of interest, and contribution to host fitness are reported for the first time.

Adaptive laboratory evolution of ethanologenic Zymomonas mobilis strain tolerant to furfural and acetic acid inhibitors.

PubMed

Shui, Zong-Xia; Qin, Han; Wu, Bo; Ruan, Zhi-yong; Wang, Lu-shang; Tan, Fu-Rong; Wang, Jing-Li; Tang, Xiao-Yu; Dai, Li-Chun; Hu, Guo-Quan; He, Ming-Xiong

2015-07-01

Furfural and acetic acid from lignocellulosic hydrolysates are the prevalent inhibitors to Zymomonas mobilis during cellulosic ethanol production. Developing a strain tolerant to furfural or acetic acid inhibitors is difficul by using rational engineering strategies due to poor understanding of their underlying molecular mechanisms. In this study, strategy of adaptive laboratory evolution (ALE) was used for development of a furfural and acetic acid-tolerant strain. After three round evolution, four evolved mutants (ZMA7-2, ZMA7-3, ZMF3-2, and ZMF3-3) that showed higher growth capacity were successfully obtained via ALE method. Based on the results of profiling of cell growth, glucose utilization, ethanol yield, and activity of key enzymes, two desired strains, ZMA7-2 and ZMF3-3, were achieved, which showed higher tolerance under 7 g/l acetic acid and 3 g/l furfural stress condition. Especially, it is the first report of Z. mobilis strain that could tolerate higher furfural. The best strain, Z. mobilis ZMF3-3, has showed 94.84% theoretical ethanol yield under 3-g/l furfural stress condition, and the theoretical ethanol yield of ZM4 is only 9.89%. Our study also demonstrated that ALE method might also be used as a powerful metabolic engineering tool for metabolic engineering in Z. mobilis. Furthermore, the two best strains could be used as novel host for further metabolic engineering in cellulosic ethanol or future biorefinery. Importantly, the two strains may also be used as novel-tolerant model organisms for the genetic mechanism on the "omics" level, which will provide some useful information for inverse metabolic engineering.

Metabolic engineering of Zymomonas mobilis for 2,3-butanediol production from lignocellulosic biomass sugars

DOE PAGES

Yang, Shihui; Mohagheghi, Ali; Franden, Mary Ann; ...

2016-09-02

To develop pathways for advanced biofuel production, and to understand the impact of host metabolism and environmental conditions on heterologous pathway engineering for economic advanced biofuels production from biomass, we seek to redirect the carbon flow of the model ethanologen Zymomonas mobilis to produce desirable hydrocarbon intermediate 2,3-butanediol (2,3-BDO). 2,3-BDO is a bulk chemical building block, and can be upgraded in high yields to gasoline, diesel, and jet fuel. 2,3-BDO biosynthesis pathways from various bacterial species were examined, which include three genes encoding acetolactate synthase, acetolactate decarboxylase, and butanediol dehydrogenase. Bioinformatics analysis was carried out to pinpoint potential bottlenecks formore » high 2,3-BDO production. Different combinations of 2,3-BDO biosynthesis metabolic pathways using genes from different bacterial species have been constructed. Our results demonstrated that carbon flux can be deviated from ethanol production into 2,3-BDO biosynthesis, and all three heterologous genes are essential to efficiently redirect pyruvate from ethanol production for high 2,3-BDO production in Z. mobilis. The down-selection of best gene combinations up to now enabled Z. mobilis to reach the 2,3-BDO production of more than 10 g/L from glucose and xylose, as well as mixed C6/C5 sugar streams derived from the deacetylation and mechanical refining process. In conclusion, this study confirms the value of integrating bioinformatics analysis and systems biology data during metabolic engineering endeavors, provides guidance for value-added chemical production in Z. mobilis, and reveals the interactions between host metabolism, oxygen levels, and a heterologous 2,3-BDO biosynthesis pathway. Taken together, this work provides guidance for future metabolic engineering efforts aimed at boosting 2,3-BDO titer anaerobically.« less

Metabolic engineering of Zymomonas mobilis for 2,3-butanediol production from lignocellulosic biomass sugars

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang, Shihui; Mohagheghi, Ali; Franden, Mary Ann

To develop pathways for advanced biofuel production, and to understand the impact of host metabolism and environmental conditions on heterologous pathway engineering for economic advanced biofuels production from biomass, we seek to redirect the carbon flow of the model ethanologen Zymomonas mobilis to produce desirable hydrocarbon intermediate 2,3-butanediol (2,3-BDO). 2,3-BDO is a bulk chemical building block, and can be upgraded in high yields to gasoline, diesel, and jet fuel. 2,3-BDO biosynthesis pathways from various bacterial species were examined, which include three genes encoding acetolactate synthase, acetolactate decarboxylase, and butanediol dehydrogenase. Bioinformatics analysis was carried out to pinpoint potential bottlenecks formore » high 2,3-BDO production. Different combinations of 2,3-BDO biosynthesis metabolic pathways using genes from different bacterial species have been constructed. Our results demonstrated that carbon flux can be deviated from ethanol production into 2,3-BDO biosynthesis, and all three heterologous genes are essential to efficiently redirect pyruvate from ethanol production for high 2,3-BDO production in Z. mobilis. The down-selection of best gene combinations up to now enabled Z. mobilis to reach the 2,3-BDO production of more than 10 g/L from glucose and xylose, as well as mixed C6/C5 sugar streams derived from the deacetylation and mechanical refining process. In conclusion, this study confirms the value of integrating bioinformatics analysis and systems biology data during metabolic engineering endeavors, provides guidance for value-added chemical production in Z. mobilis, and reveals the interactions between host metabolism, oxygen levels, and a heterologous 2,3-BDO biosynthesis pathway. Taken together, this work provides guidance for future metabolic engineering efforts aimed at boosting 2,3-BDO titer anaerobically.« less

Fermentable metabolite of Zymomonas mobilis controls collagen reduction in photoaging skin by improving TGF-beta/Smad signaling suppression.

PubMed

Tanaka, Hiroshi; Yamaba, Hiroyuki; Kosugi, Nobuhiko; Mizutani, Hiroshi; Nakata, Satoru

2008-04-01

Solar ultraviolet (UV) irradiation causes damages on human skin and premature skin aging (photoaging). UV-induced reduction of type I collagen in dermis is widely considered primarily induction of wrinkled appearance of photoaging skin. Type I procollagen synthesis is reduced under UV irradiation by blocking transforming growth factor-beta (TGF-beta)/Smad signaling; more specifically, it is down-regulation of TGF-beta type II receptor (T beta RII). Therefore, preventing UV-induced loss of T beta RII results decreased type I collagen reduction in photoaging skin. Zymomonas mobilis is an alcohol fermentable, gram-negative facultative anaerobic bacterium whose effect on skin tissue is scarcely studied. We investigated the protective effects of fermentable metabolite of Z. mobilis (FM of Z. mobilis) against reduction of type I procollagen synthesis of UV-induced down-regulation of T beta RII in human dermal fibroblasts FM of Z. mobilis was obtained from lyophilization of bacterium culture supernatant. The levels of T beta RII and type I procollagen mRNA in human dermal fibroblasts were measured by quantitative real-time RT-PCR, and T beta RII protein levels were assayed by western blotting. T beta RII, type I procollagen, and type I collagen proteins in human dermal fibroblasts or hairless mouse skin were detected by immunostaining. FM of Z. mobilis inhibited down regulation of T beta RII mRNA, and protein levels in UVB irradiated human dermal fibroblasts consequently recover reduced type I procollagen synthesis. These results indicate UVB irradiation inhibits type I procollagen synthesis by suppression of TGF-beta/Smad signaling pathway, and FM of Z. mobilis has inhibitory effect on UVB-induced reduction of type I procollagen synthesis. While short period UVB irradiation decreased both T beta RII and type I procollagen protein levels in hairless mouse skin, topical application of FM of Z. mobilis prevented this decrease. Wrinkle formation in hairless mouse skin surface was accelerated by continuous 5 month UVB irradiation along with a reduction of type I collagen in the dermis, but this change was prevented by topical application of FM of Z. mobilis. From this experimental data, it is suggested that FM of Z. mobilis is effective for suppression of wrinkle formation in photoaging skin by inhibition of type I procollagen synthesis reduction.

Bioethanol Production From Banana Stem By Using Simultaneous Saccharification and Fermentation (SSF)

NASA Astrophysics Data System (ADS)

Kusmiyati; Mustofa, A.; Jumarmi

2018-05-01

The rapid growth and development of industries in the world result in a greater energy needs. Some studies show that ethanol can be used as an alternative energy. However, bioethanol production from food raw materials such as sugar and starch has drawback that cause the food crisis. This aim of this study was to convert banana stem into bioethanol. Banana stem contained of 44.6% cellulose, 36.0% hemicellulose and 19.4% lignin. After banana stems were pretreated with acid (H2SO4) and alkaline (NaOH) at a concentration of 2% w/v at 121 °C for 30 minutes, then subsequently the simultaneous saccharification and fermentation (SSF) were carried out by using mixed cultures of Aspergillus niger, Trichoderma reesei and Zymomonas mobilis at various enzymes ratios of (1:1:1), (1:2:1), (1:2:2), (1:1:2) and various pH (4, 5 and 6) with SSF time for 144 hours and temperature of 30°C. The results show that acid pretreatment showed better results than the alkali pretreatment. After acid pretreatment and alkali pretreatment, lignin content of pretreted banana stem reduced to 15.92% and 16.34%, respectively, cellulose increased to 52.11% and 50.6% respectively, hemicellulose reduced to 28.45% and 28.83%, respectively The SSF showed that pH 5 gave the highest bioethanol. The highest concentration of bioethanol (8.51 g/L) was achieved at the SSF process at pH 5 with a ratio Aspergillus niger, Trichoderma reesei and Zymomonas mobilis enzymes of (1:1:2).

Effect of Brönsted acidic ionic liquid 1-(1-propylsulfonic)-3-methylimidazolium chloride on growth and co-fermentation of glucose, xylose and arabinose by Zymomonas mobilis AX101.

PubMed

Gyamerah, M; Ampaw-Asiedu, M; Mackey, J; Menezes, B; Woldesenbet, S

2018-06-01

The potential of large-scale lignocellulosic biomass hydrolysis to fermentable sugars using ionic liquids has increased interest in this green chemistry route to fermentation for fuel-ethanol production. The ionic liquid 1-(1-propylsulfonic)-3-methylimidazolium chloride compared to other reported ionic liquids has the advantage of hydrolysing lignocellulosic biomass to reducing sugars at catalytic concentrations (≤0·032 mol l -1 ) in a single step. However, effects of this ionic liquid on co-fermentation of glucose, xylose and arabinose to ethanol by recombinant Zymomonas mobilisAX101 has not been studied. Authentic glucose, xylose and arabinose were used to formulate fermentation media at varying catalytic 1-(1-propylsulfonic)-3-methylimidazolium chloride concentrations for batch co-fermentation of the sugars using Z. mobilisAX101. The results showed that at 0·008, 0·016 and 0·032 mol l -1 ionic liquid in the culture medium, cell growth decreased by 10, 27 and 67% respectively compared to the control. Ethanol yields were 62·6, 61·8, 50·5 and 23·1% for the control, 0·008, 0·016 and 0·032 mol l -1 ionic liquid respectively. The results indicate that lignocellulosic biomass hydrolysed using 0·008 mol l -1 of 1-(1-propylsulfonic)-3-methylimidazolium chloride would eliminate an additional separation step and provide a ready to use fermentation substrate. This is the first reported study of the effect of the Brönsted acidic ionic liquid 1-(1-propylsulfonic)-3-methylimidazolium chloride on growth and co-fermentation of glucose, xylose and arabinose by Zymomonas mobilisAX101 in batch culture. Growth on and co-fermentation of the sugars by Z. mobilisAX 101 with no significant inhibition by the ionic liquid at the same catalytic amounts of 0·008 mol l -1 used to hydrolyse lignocellulosic biomass to reducing sugars overcome two major hurdles that adversely affect the process economics of large-scale industrial cellulosic fuel ethanol production; the energy-intensive hydrolysis and ionic liquid separation steps. © 2018 The Society for Applied Microbiology.

Effect of acetic acid on ethanol production by Zymomonas mobilis mutant strains through continuous adaptation.

PubMed

Liu, Yu-Fan; Hsieh, Chia-Wen; Chang, Yao-Sheng; Wung, Being-Sun

2017-08-01

Acetic acid is a predominant by-product of lignocellulosic biofuel process, which inhibits microbial biocatalysts. Development of bacterial strains that are tolerant to acetic acid is challenging due to poor understanding of the underlying molecular mechanisms. In this study, we generated and characterized two acetic acid-tolerant strains of Zymomonas mobilis using N-methyl-N'-nitro-N-nitrosoguanidine (NTG)-acetate adaptive breeding. Two mutants, ZMA-142 and ZMA-167, were obtained, showing a significant growth rate at a concentration of 244 mM sodium acetate, while the growth of Z. mobilis ATCC 31823 were completely inhibited in presence of 195 mM sodium acetate. Our data showed that acetate-tolerance of ZMA-167 was attributed to a co-transcription of nhaA from ZMO0117, whereas the co-transcription was absent in ATCC 31823 and ZMA-142. Moreover, ZMA-142 and ZMA-167 exhibited a converstion rate (practical ethanol yield to theorical ethanol yield) of 90.16% and 86% at 195 mM acetate-pH 5 stress condition, respectively. We showed that acid adaptation of ZMA-142 and ZMA-167 to 146 mM acetate increased ZMA-142 and ZMA-167 resulted in an increase in ethanol yield by 32.21% and 21.16% under 195 mM acetate-pH 5 stress condition, respectively. The results indicate the acetate-adaptive seed culture of acetate-tolerant strains, ZMA-142 and ZMA-167, could enhance the ethanol production during fermentation.

Open fermentative production of fuel ethanol from food waste by an acid-tolerant mutant strain of Zymomonas mobilis.

PubMed

Ma, Kedong; Ruan, Zhiyong; Shui, Zongxia; Wang, Yanwei; Hu, Guoquan; He, Mingxiong

2016-03-01

The aim of present study was to develop a process for open ethanol fermentation from food waste using an acid-tolerant mutant of Zymomonas mobilis (ZMA7-2). The mutant showed strong tolerance to acid condition of food waste hydrolysate and high ethanol production performance. By optimizing fermentation parameters, ethanol fermentation with initial glucose concentration of 200 g/L, pH value around 4.0, inoculum size of 10% and without nutrient addition was considered as best conditions. Moreover, the potential of bench scales fermentation and cell reusability was also examined. The fermentation in bench scales (44 h) was faster than flask scale (48 h), and the maximum ethanol concentration and ethanol yield (99.78 g/L, 0.50 g/g) higher than that of flask scale (98.31 g/L, 0.49 g/g). In addition, the stable cell growth and ethanol production profile in five cycles successive fermentation was observed, indicating the mutant was suitable for industrial ethanol production. Copyright © 2015 Elsevier Ltd. All rights reserved.

Very high gravity ethanol and fatty acid production of Zymomonas mobilis without amino acid and vitamin.

PubMed

Wang, Haoyong; Cao, Shangzhi; Wang, William Tianshuo; Wang, Kaven Tianyv; Jia, Xianhui

2016-06-01

Very high gravity (VHG) fermentation is the mainstream technology in ethanol industry, which requires the strains be resistant to multiple stresses such as high glucose concentration, high ethanol concentration, high temperature and harsh acidic conditions. To our knowledge, it was not reported previously that any ethanol-producing microbe showed a high performance in VHG fermentations without amino acid and vitamin. Here we demonstrate the engineering of a xylose utilizing recombinant Zymomonas mobilis for VHG ethanol fermentations. The recombinant strain can produce ethanol up to 136 g/L without amino acid and vitamin with a theoretical yield of 90 %, which is significantly superior to that produced by all the reported ethanol-producing strains. The intracellular fatty acids of the bacterial were about 16 % of the bacterial dry biomass, with the ratio of ethanol:fatty acids was about 273:1 (g/g). The recombinant strain was achieved by a multivariate-modular strategy tackles with the multiple stresses which are closely linked to the ethanol productivity of Z. mobilis. The over-expression of metB/yfdZ operon enabled the growth of the recombinant Z. mobilis in a chemically defined medium without amino acid and vitamin; and the fatty acids overproduction significantly increased ethanol tolerance and ethanol production. The coupled production of ethanol with fatty acids of the Z. mobilis without amino acid and vitamin under VHG fermentation conditions may permit a significant reduction of the production cost of ethanol and microbial fatty acids.

Complete genome sequence and the expression pattern of plasmids of the model ethanologen Zymomonas mobilis ZM4 and its xylose-utilizing derivatives 8b and 2032

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang, Shihui; Vera, Jessica M.; Grass, Jeff

Zymomonas mobilis is a natural ethanologen being developed and deployed as an industrial biofuel producer. To date, eight Z. mobilis strains have been completely sequenced and found to contain 2-8 native plasmids. However, systematic verification of predicted Z. mobilis plasmid genes and their contribution to cell fitness has not been hitherto addressed. Moreover, the precise number and identities of plasmids in Z. mobilis model strain ZM4 have been unclear. The lack of functional information about plasmid genes in ZM4 impedes ongoing studies for this model biofuel-producing strain. In this study, we determined the complete chromosome and plasmid sequences of ZM4more » and its engineered xylose-utilizing derivatives 2032 and 8b. Compared to previously published and revised ZM4 chromosome sequences, the ZM4 chromosome sequence reported here contains 65 nucleotide sequence variations as well as a 2400-bp insertion. Four plasmids were identified in all three strains, with 150 plasmid genes predicted in strain ZM4 and 2032, and 153 plasmid genes predicted in strain 8b due to the insertion of heterologous DNA for expanded substrate utilization. Plasmid genes were then annotated using Blast2GO, InterProScan, and systems biology data analyses, and most genes were found to have apparent orthologs in other organisms or identifiable conserved domains. To verify plasmid gene prediction, RNA-Seq was used to map transcripts and also compare relative gene expression under various growth conditions, including anaerobic and aerobic conditions, or growth in different concentrations of biomass hydrolysates. Overall, plasmid genes were more responsive to varying hydrolysate concentrations than to oxygen availability. Additionally, our results indicated that although all plasmids were present in low copy number (about 1-2 per cell), the copy number of some plasmids varied under specific growth conditions or due to heterologous gene insertion. The complete genome of ZM4 and two xylose-utilizing derivatives is reported in this study, with an emphasis on identifying and characterizing plasmid genes. Furthermore, plasmid gene annotation, validation, expression levels at growth conditions of interest, and contribution to host fitness are reported for the first time.« less

Complete genome sequence and the expression pattern of plasmids of the model ethanologen Zymomonas mobilis ZM4 and its xylose-utilizing derivatives 8b and 2032

DOE PAGES

Yang, Shihui; Vera, Jessica M.; Grass, Jeff; ...

2018-05-02

Zymomonas mobilis is a natural ethanologen being developed and deployed as an industrial biofuel producer. To date, eight Z. mobilis strains have been completely sequenced and found to contain 2-8 native plasmids. However, systematic verification of predicted Z. mobilis plasmid genes and their contribution to cell fitness has not been hitherto addressed. Moreover, the precise number and identities of plasmids in Z. mobilis model strain ZM4 have been unclear. The lack of functional information about plasmid genes in ZM4 impedes ongoing studies for this model biofuel-producing strain. In this study, we determined the complete chromosome and plasmid sequences of ZM4more » and its engineered xylose-utilizing derivatives 2032 and 8b. Compared to previously published and revised ZM4 chromosome sequences, the ZM4 chromosome sequence reported here contains 65 nucleotide sequence variations as well as a 2400-bp insertion. Four plasmids were identified in all three strains, with 150 plasmid genes predicted in strain ZM4 and 2032, and 153 plasmid genes predicted in strain 8b due to the insertion of heterologous DNA for expanded substrate utilization. Plasmid genes were then annotated using Blast2GO, InterProScan, and systems biology data analyses, and most genes were found to have apparent orthologs in other organisms or identifiable conserved domains. To verify plasmid gene prediction, RNA-Seq was used to map transcripts and also compare relative gene expression under various growth conditions, including anaerobic and aerobic conditions, or growth in different concentrations of biomass hydrolysates. Overall, plasmid genes were more responsive to varying hydrolysate concentrations than to oxygen availability. Additionally, our results indicated that although all plasmids were present in low copy number (about 1-2 per cell), the copy number of some plasmids varied under specific growth conditions or due to heterologous gene insertion. The complete genome of ZM4 and two xylose-utilizing derivatives is reported in this study, with an emphasis on identifying and characterizing plasmid genes. Furthermore, plasmid gene annotation, validation, expression levels at growth conditions of interest, and contribution to host fitness are reported for the first time.« less

Zymomonas pentose-sugar fermenting strains and uses thereof

DOEpatents

Zhang, Min [Lakewood, CO; Chou, Yat-Chen [Golden, CO; Howe, William [Golden, CO; Eddy, Christine [Golden, CO; Evans, Kent [Littleton, CO; Mohagheghi, Ali [Northglenn, CO

2007-05-29

Disclosed in the present invention is a Zymomonas integrant and derivatives of these integrants that posses the ability to ferment pentose into ethanol. The genetic sequences encoding for the pentose-fermenting enzymes are integrated into the Zymomonas in a two-integration event of homologous recombination and transposition. Each operon includes more than one pentose-reducing enzyme encoding sequence. The integrant in some embodiments includes enzyme sequences encoding xylose isomerase, xylulokinase, transketolase and transketolase. The Zymomonas integrants are highly stable, and retain activity for producing the pentose-fermenting enzyme for between 80 to 160 generations. The integrants are also resistant to acetate inhibition, as the integrants demonstrate efficient ethanol production even in the presence of 8 up to 16 grams acetate per liter media. These stably integrated sequences provide a unique Zymomonas that may then be used for the efficient conversion of pentose sugars (xylose, arabinose) to ethanol. Method of using the Zymomonas integrants and derivatives thereof in production of ethanol from cellulosic feedstock is also disclosed. The invention also provides a method for preparing a Zymomonas integrant as part of the present invention. The host Zymomonas strain found particularly useful in the creation of these compositions and methods is Zymomonas mobilis 31821.

Impact of expression of EMP enzymes on glucose metabolism in Zymomonas mobilis.

PubMed

Chen, Rachel Ruizhen; Agrawal, Manoj; Mao, Zichao

2013-06-01

Zymomonas mobilis is the only known microorganism that utilizes the Entner-Doudoroff (ED) pathway anaerobically. In this work, we investigated whether the overexpression of a phosphofructokinase (PFK), the only missing Embden-Meyerhof-Parnas (EMP) pathway enzyme, could establish the pathway in this organism. Introduction of a pyrophosphate-dependent PFK, along with co-expression of homologous fructose-1,6-bisphosphate aldolase and triosephosphate isomerase, did not result in an EMP flux to any appreciable level. However, the metabolism of glucose was impacted significantly. Eight percent of glucose was metabolized to form a new metabolite, dihydroxyacetone. Reducing flux through the ED pathway by as much as 40 % through antisense of a key enzyme, ED aldolase, did not result in a fully functional EMP pathway, suggesting that the ED pathway, especially the lower arm, downstream from glyceraldehyde-3-phosphate, is very rigid, possibly due to redox balance.

Similarity of Escherichia coli propanediol oxidoreductase (fucO product) and an unusual alcohol dehydrogenase from Zymomonas mobilis and Saccharomyces cerevisiae

DOE Office of Scientific and Technical Information (OSTI.GOV)

Conway, T.; Ingram, L.O.

1989-07-01

The gene that encodes 1,2-propanediol oxidoreductase (fucO) from Escherichia coli was sequenced. The reading frame specified a protein of 383 amino acids (including the N-terminal methionine), with an aggregate molecular weight of 40,642. The induction of fucO transcription, which occurred in the presence of fucose, was confirmed by Northern blot analysis. In E. coli, the primary fucO transcript was approximately 2.1 kilobases in length. The 5{prime} end of the transcript began more than 0.7 kilobase upstream of the fucO start codon within or beyond the fucA gene. Propanediol oxidoreductase exhibited 41.7% identity with the iron-containing alcohol dehydrogenase II from Zymomonasmore » mobilis and 39.5% identity with ADH4 from Saccharomyces cerevisiae. These three proteins did not share homology with either short-chain or long-chain zinc-containing alcohol dehydrogenase enzymes. We propose that these three unusual alcohol dehydrogenases define a new family of enzymes.« less

Crystal structure of cbbF from Zymomonas mobilis and its functional implication

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hwang, Hyo-Jeong; Park, Suk-Youl; Kim, Jeong-Sun, E-mail: jsunkim@chonnam.ac.kr

2014-02-28

Highlights: • The crystal structure of one cbbF from Zymomonas mobilis was revealed. • Scores of residues form two secondary structures with a non-polar protruded residue. • It exists as a dimeric form in solution. - Abstract: A phosphate group at the C1-atom of inositol-monophosphate (IMP) and fructose-1,6-bisphosphate (FBP) is hydrolyzed by a phosphatase IMPase and FBPase in a metal-dependent way, respectively. The two enzymes are almost indiscernible from each other because of their highly similar sequences and structures. Metal ions are bound to residues on the β1- and β2-strands and one mobile loop. However, FBP has another phosphate andmore » FBPases exist as a higher oligomeric state, which may discriminate FBPases from IMPases. There are three genes annotated as FBPases in Zymomonas mobilis, termed also cbbF (ZmcbbF). The revealed crystal structure of one ZmcbbF shows a globular structure formed by five stacked layers. Twenty-five residues in the middle of the sequence form an α-helix and a β-strand, which occupy one side of the catalytic site. A non-polar Leu residue among them is protruded to the active site, pointing out unfavorable access of a bulky charged group to this side. In vitro assays have shown its dimeric form in solution. Interestingly, two β-strands of β1 and β2 are disordered in the ZmcbbF structure. These data indicate that ZmcbbF might structurally belong to IMPase, and imply that its active site would be reorganized in a yet unreported way.« less

Increase in Furfural Tolerance in Ethanologenic Escherichia coli LY180 by Plasmid-Based Expression of thyA

PubMed Central

Zheng, Huabao; Wang, Xuan; Yomano, Lorraine P.; Shanmugam, Keelnatham T.

2012-01-01

Furfural is an inhibitory side product formed during the depolymerization of hemicellulose by mineral acids. Genomic libraries from three different bacteria (Bacillus subtilis YB886, Escherichia coli NC3, and Zymomonas mobilis CP4) were screened for genes that conferred furfural resistance on plates. Beneficial plasmids containing the thyA gene (coding for thymidylate synthase) were recovered from all three organisms. Expression of this key gene in the de novo pathway for dTMP biosynthesis improved furfural resistance on plates and during fermentation. A similar benefit was observed by supplementation with thymine, thymidine, or the combination of tetrahydrofolate and serine (precursors for 5,10-methylenetetrahydrofolate, the methyl donor for ThyA). Supplementation with deoxyuridine provided a small benefit, and deoxyribose was of no benefit for furfural tolerance. A combination of thymidine and plasmid expression of thyA was no more effective than either alone. Together, these results demonstrate that furfural tolerance is increased by approaches that increase the supply of pyrimidine deoxyribonucleotides. However, ThyA activity was not directly affected by the addition of furfural. Furfural has been previously shown to damage DNA in E. coli and to activate a cellular response to oxidative damage in yeast. The added burden of repairing furfural-damaged DNA in E. coli would be expected to increase the cellular requirement for dTMP. Increased expression of thyA (E. coli, B. subtilis, or Z. mobilis), supplementation of cultures with thymidine, and supplementation with precursors for 5,10-methylenetetrahydrofolate (methyl donor) are each proposed to increase furfural tolerance by increasing the availability of dTMP for DNA repair. PMID:22504824

Increase in furfural tolerance in ethanologenic Escherichia coli LY180 by plasmid-based expression of thyA.

PubMed

Zheng, Huabao; Wang, Xuan; Yomano, Lorraine P; Shanmugam, Keelnatham T; Ingram, Lonnie O

2012-06-01

Furfural is an inhibitory side product formed during the depolymerization of hemicellulose by mineral acids. Genomic libraries from three different bacteria (Bacillus subtilis YB886, Escherichia coli NC3, and Zymomonas mobilis CP4) were screened for genes that conferred furfural resistance on plates. Beneficial plasmids containing the thyA gene (coding for thymidylate synthase) were recovered from all three organisms. Expression of this key gene in the de novo pathway for dTMP biosynthesis improved furfural resistance on plates and during fermentation. A similar benefit was observed by supplementation with thymine, thymidine, or the combination of tetrahydrofolate and serine (precursors for 5,10-methylenetetrahydrofolate, the methyl donor for ThyA). Supplementation with deoxyuridine provided a small benefit, and deoxyribose was of no benefit for furfural tolerance. A combination of thymidine and plasmid expression of thyA was no more effective than either alone. Together, these results demonstrate that furfural tolerance is increased by approaches that increase the supply of pyrimidine deoxyribonucleotides. However, ThyA activity was not directly affected by the addition of furfural. Furfural has been previously shown to damage DNA in E. coli and to activate a cellular response to oxidative damage in yeast. The added burden of repairing furfural-damaged DNA in E. coli would be expected to increase the cellular requirement for dTMP. Increased expression of thyA (E. coli, B. subtilis, or Z. mobilis), supplementation of cultures with thymidine, and supplementation with precursors for 5,10-methylenetetrahydrofolate (methyl donor) are each proposed to increase furfural tolerance by increasing the availability of dTMP for DNA repair.

Bioethanol production from leafy biomass of mango (Mangifera indica) involving naturally isolated and recombinant enzymes.

PubMed

Das, Saprativ P; Ravindran, Rajeev; Deka, Deepmoni; Jawed, Mohammad; Das, Debasish; Goyal, Arun

2013-01-01

The present study describes the usage of dried leafy biomass of mango (Mangifera indica) containing 26.3% (w/w) cellulose, 54.4% (w/w) hemicellulose, and 16.9% (w/w) lignin, as a substrate for bioethanol production from Zymomonas mobilis and Candida shehatae. The substrate was subjected to two different pretreatment strategies, namely, wet oxidation and an organosolv process. An ethanol concentration (1.21 g/L) was obtained with Z. mobilis in a shake-flask simultaneous saccharification and fermentation (SSF) trial using 1% (w/v) wet oxidation pretreated mango leaves along with mixed enzymatic consortium of Bacillus subtilis cellulase and recombinant hemicellulase (GH43), whereas C. shehatae gave a slightly higher (8%) ethanol titer of 1.31 g/L. Employing 1% (w/v) organosolv pretreated mango leaves and using Z. mobilis and C. shehatae separately in the SSF, the ethanol titers of 1.33 g/L and 1.52 g/L, respectively, were obtained. The SSF experiments performed with 5% (w/v) organosolv-pretreated substrate along with C. shehatae as fermentative organism gave a significantly enhanced ethanol titer value of 8.11 g/L using the shake flask and 12.33 g/L at the bioreactor level. From the bioreactor, 94.4% (v/v) ethanol was recovered by rotary evaporator with 21% purification efficiency.

Improving a recombinant Zymomonas mobilis strain 8b through continuous adaptation on dilute acid pretreated corn stover hydrolysate

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mohagheghi, Ali; Linger, Jeffrey G.; Yang, Shihui

Complete conversion of the major sugars of biomass including both the C 5 and C 6 sugars is critical for biofuel production processes. Several inhibitory compounds like acetate, hydroxymethylfurfural (HMF), and furfural are produced from the biomass pretreatment process leading to ‘hydrolysate toxicity,’ a major problem for microorganisms to achieve complete sugar utilization. Therefore, development of more robust microorganisms to utilize the sugars released from biomass under toxic environment is critical. In this study, we use continuous culture methodologies to evolve and adapt the ethanologenic bacterium Zymomonas mobilis to improve its ethanol productivity using corn stover hydrolysate. The results aremore » the following: A turbidostat was used to adapt the Z. mobilis strain 8b in the pretreated corn stover liquor. The adaptation was initiated using pure sugar (glucose and xylose) followed by feeding neutralized liquor at different dilution rates. Once the turbidostat reached 60% liquor content, the cells began washing out and the adaptation was stopped. Several ‘sub-strains’ were isolated, and one of them, SS3 (sub-strain 3), had 59% higher xylose utilization than the parent strain 8b when evaluated on 55% neutralized PCS (pretreated corn stover) liquor. Using saccharified PCS slurry generated by enzymatic hydrolysis from 25% solids loading, SS3 generated an ethanol yield of 75.5% compared to 64% for parent strain 8b. Furthermore, the total xylose utilization was 57.7% for SS3 versus 27.4% for strain 8b. To determine the underlying genotypes in these new sub-strains, we conducted genomic resequencing and identified numerous single-nucleotide mutations (SNPs) that had arisen in SS3. We further performed quantitative reverse transcription PCR (qRT-PCR) on genes potentially affected by these SNPs and identified significant down-regulation of two genes, ZMO0153 and ZMO0776, in SS3 suggesting potential genetic mechanisms behind SS3’s improved performance. In conclusion, we have adapted/evolved Z. mobilis strain 8b for enhanced tolerance to the toxic compounds present in corn stover hydrolysates. The adapted strain SS3 has higher xylose utilization rate and produce more ethanol than the parent strain. We have identified transcriptional changes which may be responsible for these phenotypes, providing foundations for future research directions in improving Z. mobilis as biocatalysts for the production of ethanol or other fuel precursors.« less

Improving a recombinant Zymomonas mobilis strain 8b through continuous adaptation on dilute acid pretreated corn stover hydrolysate

DOE PAGES

Mohagheghi, Ali; Linger, Jeffrey G.; Yang, Shihui; ...

2015-03-31

Complete conversion of the major sugars of biomass including both the C 5 and C 6 sugars is critical for biofuel production processes. Several inhibitory compounds like acetate, hydroxymethylfurfural (HMF), and furfural are produced from the biomass pretreatment process leading to ‘hydrolysate toxicity,’ a major problem for microorganisms to achieve complete sugar utilization. Therefore, development of more robust microorganisms to utilize the sugars released from biomass under toxic environment is critical. In this study, we use continuous culture methodologies to evolve and adapt the ethanologenic bacterium Zymomonas mobilis to improve its ethanol productivity using corn stover hydrolysate. The results aremore » the following: A turbidostat was used to adapt the Z. mobilis strain 8b in the pretreated corn stover liquor. The adaptation was initiated using pure sugar (glucose and xylose) followed by feeding neutralized liquor at different dilution rates. Once the turbidostat reached 60% liquor content, the cells began washing out and the adaptation was stopped. Several ‘sub-strains’ were isolated, and one of them, SS3 (sub-strain 3), had 59% higher xylose utilization than the parent strain 8b when evaluated on 55% neutralized PCS (pretreated corn stover) liquor. Using saccharified PCS slurry generated by enzymatic hydrolysis from 25% solids loading, SS3 generated an ethanol yield of 75.5% compared to 64% for parent strain 8b. Furthermore, the total xylose utilization was 57.7% for SS3 versus 27.4% for strain 8b. To determine the underlying genotypes in these new sub-strains, we conducted genomic resequencing and identified numerous single-nucleotide mutations (SNPs) that had arisen in SS3. We further performed quantitative reverse transcription PCR (qRT-PCR) on genes potentially affected by these SNPs and identified significant down-regulation of two genes, ZMO0153 and ZMO0776, in SS3 suggesting potential genetic mechanisms behind SS3’s improved performance. In conclusion, we have adapted/evolved Z. mobilis strain 8b for enhanced tolerance to the toxic compounds present in corn stover hydrolysates. The adapted strain SS3 has higher xylose utilization rate and produce more ethanol than the parent strain. We have identified transcriptional changes which may be responsible for these phenotypes, providing foundations for future research directions in improving Z. mobilis as biocatalysts for the production of ethanol or other fuel precursors.« less

Ethanol production in recombinant hosts

DOEpatents

Ingram, Lonnie O'Neal; Barbosa-Alleyne, Maria D.

2005-02-01

The subject invention concerns the transformation of Gram-positive bacteria with heterologous genes which confer upon these microbes the ability to produce ethanol as a fermentation product. Specifically exemplified is the transformation of bacteria with genes, obtainable from Zymomonas mobilis, which encode pyruvate decarboxylase and alcohol dehydrogenase.

Ethanol production in gram-positive microbes

DOEpatents

Ingram, Lonnie O'Neal; Barbosa-Alleyne, Maria D. F.

1999-01-01

The subject invention concerns the transformation of Gram-positive bacteria with heterologous genes which confer upon these microbes the ability to produce ethanol as a fermentation product. Specifically exemplified is the transformation of bacteria with genes, obtainable from Zymomonas mobilis, which encode pyruvate decarboxylase and alcohol dehydrogenase.

Ethanol production in Gram-positive microbes

DOEpatents

Ingram, Lonnie O'Neal; Barbosa-Alleyne, Maria D. F.

1996-01-01

The subject invention concerns the transformation of Gram-positive bacteria with heterologous genes which confer upon these microbes the ability to produce ethanol as a fermentation product. Specifically exemplified is the transformation of bacteria with genes, obtainable from Zymomonas mobilis, which encode pyruvate decarboxylase and alcohol dehydrogenase.

Ethanol production in Gram-positive microbes

DOEpatents

Ingram, L.O.; Barbosa-Alleyne, M.D.F.

1999-06-29

The subject invention concerns the transformation of Gram-positive bacteria with heterologous genes which confer upon these microbes the ability to produce ethanol as a fermentation product. Specifically exemplified is the transformation of bacteria with genes, obtainable from Zymomonas mobilis, which encode pyruvate decarboxylase and alcohol dehydrogenase. 2 figs.

Ethanol production in Gram-positive microbes

DOEpatents

Ingram, L.O.; Barbosa-Alleyne, M.D.F.

1996-01-09

The subject invention concerns the transformation of Gram-positive bacteria with heterologous genes which confer upon these microbes the ability to produce ethanol as a fermentation product. Specifically exemplified is the transformation of bacteria with genes, obtainable from Zymomonas mobilis, which encode pyruvate decarboxylase and alcohol dehydrogenase. 2 figs.

Rheology, fatty acid profile and quality characteristics of nutrient enriched pizza base.

PubMed

Gupta, Chaitali Sen; Milind; Jeyarani, T; Rajiv, Jyotsna

2015-05-01

Enrichment of thick bread type pizza base (PZB) was done by substituting wheat flour (WF) with 5, 10 and 15 % soya protein isolate (SPI). The rheological characteristics of WF showed that water absorption increased, extensibility and peak viscosity decreased when level of SPI increased from 5 to 15 %. Baking studies showed that spread ratio decreased and hardness values of PZB increased with the increase in amount of SPI from 5 to15 %. Beyond 10 % SPI, the overall quality of PZB was adversely affected. To the optimal blend of 10 % SPI, 5 % psyllium husk (PH) was added and the hydrogenated fat was replaced by canola oil (CAN) in enriched PZB. The enriched PZB treated with combination of additives had 1.7 and 1.6 times more protein and dietary fiber than the control PZB. Fatty acid analysis showed that the enriched PZB had 58.65 % oleic, 6.58 % linolenic acid and 31.28 % polyunsaturated fatty acid and no Trans fat was present.

Biological conversion system

DOEpatents

Scott, C.D.

A system for bioconversion of organic material comprises a primary bioreactor column wherein a biological active agent (zymomonas mobilis) converts the organic material (sugar) to a product (alcohol), a rejuvenator column wherein the biological activity of said biological active agent is enhanced, and means for circulating said biological active agent between said primary bioreactor column and said rejuvenator column.

Dissecting a complex chemical stress: chemogenomic profiling of plant hydrolysates

PubMed Central

Skerker, Jeffrey M; Leon, Dacia; Price, Morgan N; Mar, Jordan S; Tarjan, Daniel R; Wetmore, Kelly M; Deutschbauer, Adam M; Baumohl, Jason K; Bauer, Stefan; Ibáñez, Ana B; Mitchell, Valerie D; Wu, Cindy H; Hu, Ping; Hazen, Terry; Arkin, Adam P

2013-01-01

The efficient production of biofuels from cellulosic feedstocks will require the efficient fermentation of the sugars in hydrolyzed plant material. Unfortunately, plant hydrolysates also contain many compounds that inhibit microbial growth and fermentation. We used DNA-barcoded mutant libraries to identify genes that are important for hydrolysate tolerance in both Zymomonas mobilis (44 genes) and Saccharomyces cerevisiae (99 genes). Overexpression of a Z. mobilis tolerance gene of unknown function (ZMO1875) improved its specific ethanol productivity 2.4-fold in the presence of miscanthus hydrolysate. However, a mixture of 37 hydrolysate-derived inhibitors was not sufficient to explain the fitness profile of plant hydrolysate. To deconstruct the fitness profile of hydrolysate, we profiled the 37 inhibitors against a library of Z. mobilis mutants and we modeled fitness in hydrolysate as a mixture of fitness in its components. By examining outliers in this model, we identified methylglyoxal as a previously unknown component of hydrolysate. Our work provides a general strategy to dissect how microbes respond to a complex chemical stress and should enable further engineering of hydrolysate tolerance. PMID:23774757

Sequence and genetic organization of a Zymomonas mobilis gene cluster that encodes several enzymes of glucose metabolism

DOE Office of Scientific and Technical Information (OSTI.GOV)

Barnell, W.O.; Kyung Cheol Yi; Conway, T.

1990-12-01

The Zymomonas mobilis genes that encode glucose-6-phosphate dehydrogenase (zwf), 6-phosphogluconate dehydratase (edd), and glucokinase (glk) were cloned independently by genetic complementation of specific defects in Escherichia coli metabolism. The identify of these cloned genes was confirmed by various biochemical means. Nucleotide sequence analysis established that these three genes are clustered on the genome and revealed an additional open reading frame in this region that has significant amino acid identity to the E.coli xylose-proton symporter and the human glucose transporter. On the basis of this evidence and structural analysis of the deduced primary amino acid sequence, this gene is believed tomore » encode the Z. mobilis glucose-facilitated diffusion protein, glf. The four genes in the 6-kb cluster are organized in the order glf, zwf, edd, glk. The glf and zwf genes are separated by 146 bp. The zwf and edd genes overlap by 8 bp, and their expression may be translationally coupled. The edd and glk genes are separated by 203 bp. The glk gene is followed by tandem transcriptional terminators. The four genes appear to be organized in an operon. Such an arrangement of the genes that govern glucose uptake and the first three steps of the Entner-Doudoroff glycolytic pathway provides the organism with a mechanism for carefully regulating the levels of the enzymes that control carbon flux into the pathway.« less

Structure of the Zymomonas mobilis respiratory chain: oxygen affinity of electron transport and the role of cytochrome c peroxidase.

PubMed

Balodite, Elina; Strazdina, Inese; Galinina, Nina; McLean, Samantha; Rutkis, Reinis; Poole, Robert K; Kalnenieks, Uldis

2014-09-01

The genome of the ethanol-producing bacterium Zymomonas mobilis encodes a bd-type terminal oxidase, cytochrome bc1 complex and several c-type cytochromes, yet lacks sequences homologous to any of the known bacterial cytochrome c oxidase genes. Recently, it was suggested that a putative respiratory cytochrome c peroxidase, receiving electrons from the cytochrome bc1 complex via cytochrome c552, might function as a peroxidase and/or an alternative oxidase. The present study was designed to test this hypothesis, by construction of a cytochrome c peroxidase mutant (Zm6-perC), and comparison of its properties with those of a mutant defective in the cytochrome b subunit of the bc1 complex (Zm6-cytB). Disruption of the cytochrome c peroxidase gene (ZZ60192) caused a decrease of the membrane NADH peroxidase activity, impaired the resistance of growing culture to exogenous hydrogen peroxide and hampered aerobic growth. However, this mutation did not affect the activity or oxygen affinity of the respiratory chain, or the kinetics of cytochrome d reduction. Furthermore, the peroxide resistance and membrane NADH peroxidase activity of strain Zm6-cytB had not decreased, but both the oxygen affinity of electron transport and the kinetics of cytochrome d reduction were affected. It is therefore concluded that the cytochrome c peroxidase does not terminate the cytochrome bc1 branch of Z. mobilis, and that it is functioning as a quinol peroxidase. © 2014 The Authors.

Towards an informative mutant phenotype for every bacterial gene

DOE PAGES

Deutschbauer, Adam; Price, Morgan N.; Wetmore, Kelly M.; ...

2014-08-11

Mutant phenotypes provide strong clues to the functions of the underlying genes and could allow annotation of the millions of sequenced yet uncharacterized bacterial genes. However, it is not known how many genes have a phenotype under laboratory conditions, how many phenotypes are biologically interpretable for predicting gene function, and what experimental conditions are optimal to maximize the number of genes with a phenotype. To address these issues, we measured the mutant fitness of 1,586 genes of the ethanol-producing bacterium Zymomonas mobilis ZM4 across 492 diverse experiments and found statistically significant phenotypes for 89% of all assayed genes. Thus, inmore » Z. mobilis, most genes have a functional consequence under laboratory conditions. We demonstrate that 41% of Z. mobilis genes have both a strong phenotype and a similar fitness pattern (cofitness) to another gene, and are therefore good candidates for functional annotation using mutant fitness. Among 502 poorly characterized Z. mobilis genes, we identified a significant cofitness relationship for 174. For 57 of these genes without a specific functional annotation, we found additional evidence to support the biological significance of these gene-gene associations, and in 33 instances, we were able to predict specific physiological or biochemical roles for the poorly characterized genes. Last, we identified a set of 79 diverse mutant fitness experiments in Z. mobilis that are nearly as biologically informative as the entire set of 492 experiments. Therefore, our work provides a blueprint for the functional annotation of diverse bacteria using mutant fitness.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Deutschbauer, Adam; Price, Morgan N.; Wetmore, Kelly M.

Mutant phenotypes provide strong clues to the functions of the underlying genes and could allow annotation of the millions of sequenced yet uncharacterized bacterial genes. However, it is not known how many genes have a phenotype under laboratory conditions, how many phenotypes are biologically interpretable for predicting gene function, and what experimental conditions are optimal to maximize the number of genes with a phenotype. To address these issues, we measured the mutant fitness of 1,586 genes of the ethanol-producing bacterium Zymomonas mobilis ZM4 across 492 diverse experiments and found statistically significant phenotypes for 89% of all assayed genes. Thus, inmore » Z. mobilis, most genes have a functional consequence under laboratory conditions. We demonstrate that 41% of Z. mobilis genes have both a strong phenotype and a similar fitness pattern (cofitness) to another gene, and are therefore good candidates for functional annotation using mutant fitness. Among 502 poorly characterized Z. mobilis genes, we identified a significant cofitness relationship for 174. For 57 of these genes without a specific functional annotation, we found additional evidence to support the biological significance of these gene-gene associations, and in 33 instances, we were able to predict specific physiological or biochemical roles for the poorly characterized genes. Last, we identified a set of 79 diverse mutant fitness experiments in Z. mobilis that are nearly as biologically informative as the entire set of 492 experiments. Therefore, our work provides a blueprint for the functional annotation of diverse bacteria using mutant fitness.« less

Insights into Acetate Toxicity in Zymomonas mobilis 8b using Different Substrates

DOE PAGES

Yang, Shihui; Franden, M. A.; Brown, S. D.; ...

2014-09-30

The lignocellulosic biomass is a promising renewable feedstock for biofuel production. Acetate is one of the major inhibitors liberated from hemicelluloses during hydrolysis. Likewise, an understanding of the toxic effects of acetate on the fermentation microorganism and the efficient utilization of mixed sugars of glucose and xylose in the presence of hydrolysate inhibitors is crucial for economic biofuel production.

Stable zymomonas mobilis xylose and arabinose fermenting strains

DOEpatents

Zhang, Min [Lakewood, CO; Chou, Yat-Chen [Taipei, TW

2008-04-08

The present invention briefly includes a transposon for stable insertion of foreign genes into a bacterial genome, comprising at least one operon having structural genes encoding enzymes selected from the group consisting of xylAxylB, araBAD and tal/tkt, and at least one promoter for expression of the structural genes in the bacterium, a pair of inverted insertion sequences, the operons contained inside the insertion sequences, and a transposase gene located outside of the insertion sequences. A plasmid shuttle vector for transformation of foreign genes into a bacterial genome, comprising at least one operon having structural genes encoding enzymes selected from the group consisting of xylAxylB, araBAD and tal/tkt, at least one promoter for expression of the structural genes in the bacterium, and at least two DNA fragments having homology with a gene in the bacterial genome to be transformed, is also provided.The transposon and shuttle vectors are useful in constructing significantly different Zymomonas mobilis strains, according to the present invention, which are useful in the conversion of the cellulose derived pentose sugars into fuels and chemicals, using traditional fermentation technology, because they are stable for expression in a non-selection medium.

Optical mapping and sequencing of the Escherichia coli KO11 genome reveal extensive chromosomal rearrangements, and multiple tandem copies of the Zymomonas mobilis pdc and adhB genes.

PubMed

Turner, Peter C; Yomano, Lorraine P; Jarboe, Laura R; York, Sean W; Baggett, Christy L; Moritz, Brélan E; Zentz, Emily B; Shanmugam, K T; Ingram, Lonnie O

2012-04-01

Escherichia coli KO11 (ATCC 55124) was engineered in 1990 to produce ethanol by chromosomal insertion of the Zymomonas mobilis pdc and adhB genes into E. coli W (ATCC 9637). KO11FL, our current laboratory version of KO11, and its parent E. coli W were sequenced, and contigs assembled into genomic sequences using optical NcoI restriction maps as templates. E. coli W contained plasmids pRK1 (102.5 kb) and pRK2 (5.4 kb), but KO11FL only contained pRK2. KO11FL optical maps made with AflII and with BamHI showed a tandem repeat region, consisting of at least 20 copies of a 10-kb unit. The repeat region was located at the insertion site for the pdc, adhB, and chloramphenicol-resistance genes. Sequence coverage of these genes was about 25-fold higher than average, consistent with amplification of the foreign genes that were inserted as circularized DNA. Selection for higher levels of chloramphenicol resistance originally produced strains with higher pdc and adhB expression, and hence improved fermentation performance, by increasing the gene copy number. Sequence data for an earlier version of KO11, ATCC 55124, indicated that multiple copies of pdc adhB were present. Comparison of the W and KO11FL genomes showed large inversions and deletions in KO11FL, mostly enabled by IS10, which is absent from W but present at 30 sites in KO11FL. The early KO11 strain ATCC 55124 had no rearrangements, contained only one IS10, and lacked most accumulated single nucleotide polymorphisms (SNPs) present in KO11FL. Despite rearrangements and SNPs in KO11FL, fermentation performance was equal to that of ATCC 55124.

Development of a high-throughput method to evaluate the impact of inhibitory compounds from lignocellulosic hydrolysates on the growth of Zymomonas mobilis.

PubMed

Franden, Mary Ann; Pienkos, Philip T; Zhang, Min

2009-12-01

Overcoming the effects of hydrolysate toxicity towards ethanologens is a key technical barrier in the biochemical conversion process for biomass feedstocks to ethanol. Despite its importance, the complexity of the hydrolysate toxicity phenomena and the lack of systematic studies, analysis and tools surrounding this issue have blocked a full understanding of relationships involving toxic compounds in hydrolysates and their effects on ethanologen growth and fermentation. In this study, we developed a quantitative, high-throughput biological growth assay using an automated turbidometer to obtain detailed inhibitory kinetics for individual compounds present in lignocellulosic biomass hydrolysate. Information about prolonged lag time and final cell densities can also be obtained. The effects of furfural, hydroxymethylfurfural (HMF), acetate and ethanol on growth rate and final cell densities of Zymomonas mobilis 8b on glucose are presented. This method was also shown to be of value in toxicity studies of hydrolysate itself, despite the highly colored nature of this material. Using this approach, we can generate comprehensive inhibitory profiles with many individual compounds and develop models that predict and examine toxic effects in the complex mixture of hydrolysates, leading to the development of improved pretreatment and conditioning processes as well as fermentation organisms.

Biotransformation of pineapple juice sugars into dietetic derivatives by using a cell free oxidoreductase from Zymomonas mobilis together with commercial invertase.

PubMed

Aziz, M G; Michlmayr, H; Kulbe, K D; Del Hierro, A M

2011-01-05

An easy procedure for cell free biotransformation of pineapple juice sugars into dietetic derivatives was accomplished using a commercial invertase and an oxidoreductase from Zymomonas mobilis. First, pineapple juice sucrose was quantitatively converted into glucose and fructose by invertase, thus increasing the concentration of each monosaccharide in the original juice to almost twice. In a second step, glucose-fructose oxidoreductase (GFOR) transformed glucose into gluconolactone, and fructose into the low calorie sweetener sorbitol. The advantage of using GFOR is simultaneous reduction of fructose and oxidation of glucose, allowing the continuous regeneration of the essential coenzyme NADP(H), that is tightly bound to the enzyme. The yield of GFOR catalyzed sugar conversion depends on initial pH and control of pH during the reaction. At optimal conditions (pH control at 6.2) a maximum of 80% (w/v) sugar conversion was obtained. Without pH control, GFOR is inactivated rapidly due to gluconic acid formation. Therefore, conversion yields are relatively low at the natural pH of pineapple juice. The application of this process might be more advantageous on juices of other tropical fruits (papaya, jackfruit, mango) due to their naturally given higher pH. Copyright © 2010 Elsevier Inc. All rights reserved.

Purification and characterization of an oxygen-labile, NAD-dependent alcohol dehydrogenase from Desulfovibrio gigas.

PubMed Central

Hensgens, C M; Vonck, J; Van Beeumen, J; van Bruggen, E F; Hansen, T A

1993-01-01

A NAD-dependent, oxygen-labile alcohol dehydrogenase was purified from Desulfovibrio gigas. It was decameric, with subunits of M(r) 43,000. The best substrates were ethanol (Km, 0.15 mM) and 1-propanol (Km, 0.28 mM). N-terminal amino acid sequence analysis showed that the enzyme belongs to the same family of alcohol dehydrogenases as Zymomonas mobilis ADH2 and Bacillus methanolicus MDH. Images PMID:8491707

Bio-based extraction and stabilization of anthocyanins.

PubMed

Roy, Anirban; Mukherjee, Rudra Palash; Howard, Luke; Beitle, Robert

2016-05-01

This work reports a novel method of recovering anthocyanin compounds from highly-pigmented grapes via a fermentation based approach. It was hypothesized that batch growth of Zymomonas mobilis on simple medium would produce both ethanol and enzymes/biomass-acting materials, the combination of which will provide a superior extraction when compared to simple alcohol extraction. To examine this hypothesis, Z. mobilis was fermented in a batch consisting of mashed Vitis vinifera and glucose, and the recovered anthocyanin pool was compared to that recovered via extraction with ethanol. Data indicated higher amounts of anthocyanins were recovered when compared to simple solvent addition. Additionally, the percent polymeric form of the anthocyanins could be manipulated by the level of aeration maintained in the fermentation. © 2016 American Institute of Chemical Engineers Biotechnol. Prog., 32:601-605, 2016. © 2016 American Institute of Chemical Engineers.

Exometabolomics Assisted Design and Validation of Synthetic Obligate Mutualism

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kosina, Suzanne M.; Danielewicz, Megan A.; Mohammed, Mujahid

Synthetic microbial ecology has the potential to enhance the productivity and resiliency of biotechnology processes compared to approaches using single isolates. Engineering microbial consortia is challenging; however, one approach that has attracted significant attention is the creation of synthetic obligate mutualism using auxotrophic mutants that depend on each other for exchange or cross-feeding of metabolites. In this paper, we describe the integration of mutant library fitness profiling with mass spectrometry based exometabolomics as a method for constructing synthetic mutualism based on cross-feeding. Two industrially important species lacking known ecological interactions, Zymomonas mobilis and Escherichia coli, were selected as the testmore » species. Amino acid exometabolites identified in the spent medium of Z. mobilis were used to select three corresponding E. coli auxotrophs (proA, pheA and IlvA), as potential E. coli counterparts for the coculture. A pooled mutant fitness assay with a Z. mobilis transposon mutant library was used to identify mutants with improved growth in the presence of E. coli. An auxotroph mutant in a gene (ZMO0748) with sequence similarity to cysteine synthase A (cysK), was selected as the Z. mobilis counterpart for the coculture. Exometabolomic analysis of spent E. coli medium identified glutathione related metabolites as potentially available for rescue of the Z. mobilis cysteine synthase mutant. Three sets of cocultures between the Z. mobilis auxotroph and each of the three E. coli auxotrophs were monitored by optical density for growth and analyzed by flow cytometry to confirm high cell counts for each species. Taken together, our methods provide a technological framework for creating synthetic mutualisms combining existing screening based methods and exometabolomics for both the selection of obligate mutualism partners and elucidation of metabolites involved in auxotroph rescue.« less

Exometabolomics Assisted Design and Validation of Synthetic Obligate Mutualism

DOE PAGES

Kosina, Suzanne M.; Danielewicz, Megan A.; Mohammed, Mujahid; ...

2016-02-17

Synthetic microbial ecology has the potential to enhance the productivity and resiliency of biotechnology processes compared to approaches using single isolates. Engineering microbial consortia is challenging; however, one approach that has attracted significant attention is the creation of synthetic obligate mutualism using auxotrophic mutants that depend on each other for exchange or cross-feeding of metabolites. In this paper, we describe the integration of mutant library fitness profiling with mass spectrometry based exometabolomics as a method for constructing synthetic mutualism based on cross-feeding. Two industrially important species lacking known ecological interactions, Zymomonas mobilis and Escherichia coli, were selected as the testmore » species. Amino acid exometabolites identified in the spent medium of Z. mobilis were used to select three corresponding E. coli auxotrophs (proA, pheA and IlvA), as potential E. coli counterparts for the coculture. A pooled mutant fitness assay with a Z. mobilis transposon mutant library was used to identify mutants with improved growth in the presence of E. coli. An auxotroph mutant in a gene (ZMO0748) with sequence similarity to cysteine synthase A (cysK), was selected as the Z. mobilis counterpart for the coculture. Exometabolomic analysis of spent E. coli medium identified glutathione related metabolites as potentially available for rescue of the Z. mobilis cysteine synthase mutant. Three sets of cocultures between the Z. mobilis auxotroph and each of the three E. coli auxotrophs were monitored by optical density for growth and analyzed by flow cytometry to confirm high cell counts for each species. Taken together, our methods provide a technological framework for creating synthetic mutualisms combining existing screening based methods and exometabolomics for both the selection of obligate mutualism partners and elucidation of metabolites involved in auxotroph rescue.« less

Exometabolomics Assisted Design and Validation of Synthetic Obligate Mutualism.

PubMed

Kosina, Suzanne M; Danielewicz, Megan A; Mohammed, Mujahid; Ray, Jayashree; Suh, Yumi; Yilmaz, Suzan; Singh, Anup K; Arkin, Adam P; Deutschbauer, Adam M; Northen, Trent R

2016-07-15

Synthetic microbial ecology has the potential to enhance the productivity and resiliency of biotechnology processes compared to approaches using single isolates. Engineering microbial consortia is challenging; however, one approach that has attracted significant attention is the creation of synthetic obligate mutualism using auxotrophic mutants that depend on each other for exchange or cross-feeding of metabolites. Here, we describe the integration of mutant library fitness profiling with mass spectrometry based exometabolomics as a method for constructing synthetic mutualism based on cross-feeding. Two industrially important species lacking known ecological interactions, Zymomonas mobilis and Escherichia coli, were selected as the test species. Amino acid exometabolites identified in the spent medium of Z. mobilis were used to select three corresponding E. coli auxotrophs (proA, pheA and IlvA), as potential E. coli counterparts for the coculture. A pooled mutant fitness assay with a Z. mobilis transposon mutant library was used to identify mutants with improved growth in the presence of E. coli. An auxotroph mutant in a gene (ZMO0748) with sequence similarity to cysteine synthase A (cysK), was selected as the Z. mobilis counterpart for the coculture. Exometabolomic analysis of spent E. coli medium identified glutathione related metabolites as potentially available for rescue of the Z. mobilis cysteine synthase mutant. Three sets of cocultures between the Z. mobilis auxotroph and each of the three E. coli auxotrophs were monitored by optical density for growth and analyzed by flow cytometry to confirm high cell counts for each species. Taken together, our methods provide a technological framework for creating synthetic mutualisms combining existing screening based methods and exometabolomics for both the selection of obligate mutualism partners and elucidation of metabolites involved in auxotroph rescue.

A Highly Active Endo-Levanase BT1760 of a Dominant Mammalian Gut Commensal Bacteroides thetaiotaomicron Cleaves Not Only Various Bacterial Levans, but Also Levan of Timothy Grass

PubMed Central

Vija, Heiki; Aasamets, Anneli; Viigand, Katrin

2017-01-01

Bacteroides thetaiotaomicron, an abundant commensal of the human gut, degrades numerous complex carbohydrates. Recently, it was reported to grow on a β-2,6-linked polyfructan levan produced by Zymomonas mobilis degrading the polymer into fructooligosaccharides (FOS) with a cell surface bound endo-levanase BT1760. The FOS are consumed by B. thetaiotaomicron, but also by other gut bacteria, including health-promoting bifidobacteria and lactobacilli. Here we characterize biochemical properties of BT1760, including the activity of BT1760 on six bacterial levans synthesized by the levansucrase Lsc3 of Pseudomonas syringae pv. tomato, its mutant Asp300Asn, levansucrases of Zymomonas mobilis, Erwinia herbicola, Halomonas smyrnensis as well as on levan isolated from timothy grass. For the first time a plant levan is shown as a perfect substrate for an endo-fructanase of a human gut bacterium. BT1760 degraded levans to FOS with degree of polymerization from 2 to 13. At optimal reaction conditions up to 1 g of FOS were produced per 1 mg of BT1760 protein. Low molecular weight (<60 kDa) levans, including timothy grass levan and levan synthesized from sucrose by the Lsc3Asp300Asn, were degraded most rapidly whilst levan produced by Lsc3 from raffinose least rapidly. BT1760 catalyzed finely at human body temperature (37°C) and in moderately acidic environment (pH 5–6) that is typical for the gut lumen. According to differential scanning fluorimetry, the Tm of the endo-levanase was 51.5°C. All tested levans were sufficiently stable in acidic conditions (pH 2.0) simulating the gastric environment. Therefore, levans of both bacterial and plant origin may serve as a prebiotic fiber for B. thetaiotaomicron and contribute to short-chain fatty acids synthesis by gut microbiota. In the genome of Bacteroides xylanisolvens of human origin a putative levan degradation locus was disclosed. PMID:28103254

A Highly Active Endo-Levanase BT1760 of a Dominant Mammalian Gut Commensal Bacteroides thetaiotaomicron Cleaves Not Only Various Bacterial Levans, but Also Levan of Timothy Grass.

PubMed

Mardo, Karin; Visnapuu, Triinu; Vija, Heiki; Aasamets, Anneli; Viigand, Katrin; Alamäe, Tiina

2017-01-01

Bacteroides thetaiotaomicron, an abundant commensal of the human gut, degrades numerous complex carbohydrates. Recently, it was reported to grow on a β-2,6-linked polyfructan levan produced by Zymomonas mobilis degrading the polymer into fructooligosaccharides (FOS) with a cell surface bound endo-levanase BT1760. The FOS are consumed by B. thetaiotaomicron, but also by other gut bacteria, including health-promoting bifidobacteria and lactobacilli. Here we characterize biochemical properties of BT1760, including the activity of BT1760 on six bacterial levans synthesized by the levansucrase Lsc3 of Pseudomonas syringae pv. tomato, its mutant Asp300Asn, levansucrases of Zymomonas mobilis, Erwinia herbicola, Halomonas smyrnensis as well as on levan isolated from timothy grass. For the first time a plant levan is shown as a perfect substrate for an endo-fructanase of a human gut bacterium. BT1760 degraded levans to FOS with degree of polymerization from 2 to 13. At optimal reaction conditions up to 1 g of FOS were produced per 1 mg of BT1760 protein. Low molecular weight (<60 kDa) levans, including timothy grass levan and levan synthesized from sucrose by the Lsc3Asp300Asn, were degraded most rapidly whilst levan produced by Lsc3 from raffinose least rapidly. BT1760 catalyzed finely at human body temperature (37°C) and in moderately acidic environment (pH 5-6) that is typical for the gut lumen. According to differential scanning fluorimetry, the Tm of the endo-levanase was 51.5°C. All tested levans were sufficiently stable in acidic conditions (pH 2.0) simulating the gastric environment. Therefore, levans of both bacterial and plant origin may serve as a prebiotic fiber for B. thetaiotaomicron and contribute to short-chain fatty acids synthesis by gut microbiota. In the genome of Bacteroides xylanisolvens of human origin a putative levan degradation locus was disclosed.

Performance testing of Zymomonas mobilis metabolically engineered for cofermentation of glucose, xylose, and arabinose.

PubMed

Lawford, Hugh G; Rousseau, Joyce D

2002-01-01

IOGEN Corporation of Ottawa, Canada, has recently built a 40t/d biomass-to-ethanol demonstration plant adjacent to its enzyme production facility. It has partnered with the University of Toronto to test the C6/C5 cofermenta-tion performance characteristics of the National Renewable Energy Labora-tory's metabolically engineered Zymomonas mobilis using various biomass hydrolysates. IOGEN's feedstocks are primarily agricultural wastes such as corn stover and wheat straw. Integrated recombinant Z. mobilis strain AX101 grows on D-xylose and/or L-arabinose as the sole carbon/energy sources and ferments these pentose sugars to ethanol in high yield. Strain AX101 lacks the tetracycline resistance gene that was a common feature of other recombinant Zm constructs. Genomic integration provides reliable cofermentation performance in the absence of antibiotics, another characteristic making strain AX101 attractive for industrial cellulosic ethanol production. In this work, IOGEN's biomass hydrolysate was simulated by a pure sugar medium containing 6% (w/v) glucose, 3% xylose, and 0.35% arabinose. At a level of 3 g/L (dry solids), corn steep liquor with inorganic nitrogen (0.8 g/L of ammonium chloride or 1.2 g/L of diammonium phosphate) was a cost-effective nutritional supplement. In the absence of acetic acid, the maximum volumetric ethanol productivity of a continuous fermentation at pH 5.0 was 3.54 g/L x h. During prolonged continuous fermentation, the efficiency of sugar-to-ethanol conversion (based on total sugar load) was maintained at >85%. At a level of 0.25% (w/v) acetic acid, the productivity decreased to 1.17 g/L x h at pH 5.5. Unlike integrated, xylose-utilizing rec Zm strain C25, strain AX101 produces less lactic acid as byproduct, owing to the fact that the Escherichia coli arabinose genes are inserted into a region of the host chromosome tentatively assigned to the gene for D-lactic acid dehydrogenase. In pH-controlled batch fermentations with sugar mixtures, the order of sugar exhaustion from the medium was glucose followed by xylose and arabinose. Both the total sugar load and the sugar ratio were shown to be important determinants for efficient cofermentation. Ethanol at a level of 3% (w/v) was implicated as both inhibitory to pentose fermentation and as a potentiator of acetic acid inhibition of pentose fermentation at pH 5.5. The effect of ethanol may have been underestimated in other assessments of acetic acid sensitivity. This work underscores the importance of employing similar assay conditions in making comparative assessments of biocatalyst fermentation performance.

Starch saccharification and fermentation of uncooked sweet potato roots for fuel ethanol production.

PubMed

Zhang, Peng; Chen, Caifa; Shen, Yanhu; Ding, Tielin; Ma, Daifu; Hua, Zichun; Sun, Dongxu

2013-01-01

An energy-saving ethanol fermentation technology was developed using uncooked fresh sweet potato as raw material. A mutant strain of Aspergillus niger isolated from mildewed sweet potato was used to produce abundant raw starch saccharification enzymes for treating uncooked sweet potato storage roots. The viscosity of the fermentation paste of uncooked sweet potato roots was lower than that of the cooked roots. The ethanol fermentation was carried out by Zymomonas mobilis, and 14.4 g of ethanol (87.2% of the theoretical yield) was produced from 100g of fresh sweet potato storage roots. Based on this method, an energy-saving, high efficient and environment-friendly technology can be developed for large-scale production of fuel ethanol from sweet potato roots. Copyright © 2012 Elsevier Ltd. All rights reserved.

Heterologous Expression of Plant Cell Wall Degrading Enzymes for Effective Production of Cellulosic Biofuels

PubMed Central

Jung, Sang-Kyu; Parisutham, Vinuselvi; Jeong, Seong Hun; Lee, Sung Kuk

2012-01-01

A major technical challenge in the cost-effective production of cellulosic biofuel is the need to lower the cost of plant cell wall degrading enzymes (PCDE), which is required for the production of sugars from biomass. Several competitive, low-cost technologies have been developed to produce PCDE in different host organisms such as Escherichia coli, Zymomonas mobilis, and plant. Selection of an ideal host organism is very important, because each host organism has its own unique features. Synthetic biology-aided tools enable heterologous expression of PCDE in recombinant E. coli or Z. mobilis and allow successful consolidated bioprocessing (CBP) in these microorganisms. In-planta expression provides an opportunity to simplify the process of enzyme production and plant biomass processing and leads to self-deconstruction of plant cell walls. Although the future of currently available technologies is difficult to predict, a complete and viable platform will most likely be available through the integration of the existing approaches with the development of breakthrough technologies. PMID:22911272

Conditioning of dilute-acid pretreated corn stover hydrolysate liquors by treatment with lime or ammonium hydroxide to improve conversion of sugars to ethanol.

PubMed

Jennings, Edward W; Schell, Daniel J

2011-01-01

Dilute-acid pretreatment of lignocellulosic biomass enhances the ability of enzymes to hydrolyze cellulose to glucose, but produces many toxic compounds that inhibit fermentation of sugars to ethanol. The objective of this study was to compare the effectiveness of treating hydrolysate liquor with Ca(OH)2 and NH4OH for improving ethanol yields. Corn stover was pretreated in a pilot-scale reactor and then the liquor fraction (hydrolysate) was extracted and treated with various amounts of Ca(OH)2 or NH4OH at several temperatures. Glucose and xylose in the treated liquor were fermented to ethanol using a glucose-xylose fermenting bacteria, Zymomonas mobilis 8b. Sugar losses up to 10% occurred during treatment with Ca(OH)2, but these losses were two to fourfold lower with NH4OH treatment. Ethanol yields for NH4OH-treated hydrolysate were 33% greater than those achieved in Ca(OH)2-treated hydrolysate and pH adjustment to either 6.0 or 8.5 with NH4OH prior to fermentation produced equivalent ethanol yields. Copyright © 2010 Elsevier Ltd. All rights reserved.

From lin-benzoguanines to lin-benzohypoxanthines as ligands for Zymomonas mobilis tRNA-guanine transglycosylase: replacement of protein-ligand hydrogen bonding by importing water clusters.

PubMed

Barandun, Luzi Jakob; Immekus, Florian; Kohler, Philipp C; Tonazzi, Sandro; Wagner, Björn; Wendelspiess, Severin; Ritschel, Tina; Heine, Andreas; Kansy, Manfred; Klebe, Gerhard; Diederich, François

2012-07-23

The foodborne illness shigellosis is caused by Shigella bacteria that secrete the highly cytotoxic Shiga toxin, which is also formed by the closely related enterohemorrhagic Escherichia coli (EHEC). It has been shown that tRNA-guanine transglycosylase (TGT) is essential for the pathogenicity of Shigella flexneri. Herein, the molecular recognition properties of a guanine binding pocket in Zymomonas mobilis TGT are investigated with a series of lin-benzohypoxanthine- and lin-benzoguanine-based inhibitors that bear substituents to occupy either the ribose-33 or the ribose-34 pocket. The three inhibitor scaffolds differ by the substituent at C(6) being H, NH(2), or NH-alkyl. These differences lead to major changes in the inhibition constants, pK(a) values, and binding modes. Compared to the lin-benzoguanines, with an exocyclic NH(2) at C(6), the lin-benzohypoxanthines without an exocyclic NH(2) group have a weaker affinity as several ionic protein-ligand hydrogen bonds are lost. X-ray cocrystal structure analysis reveals that a new water cluster is imported into the space vacated by the lacking NH(2) group and by a conformational shift of the side chain of catalytic Asp102. In the presence of an N-alkyl group at C(6) in lin-benzoguanine ligands, this water cluster is largely maintained but replacement of one of the water molecules in the cluster leads to a substantial loss in binding affinity. This study provides new insight into the role of water clusters at enzyme active sites and their challenging substitution by ligand parts, a topic of general interest in contemporary structure-based drug design. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Novel reaction for new fuels

DOE Office of Scientific and Technical Information (OSTI.GOV)

Clyde, R.A.

Independent investigators have found that sugar can be fermented to alcohol for gasohol in 15 minutes by immobilizing organisms such as Zymomonas mobilis on rotating fibers. Half a pound of Celite has the surface area of a football field and it can be entrapped in the fibers to hold many cells. Many others take several hours. In another design, methanol can be dissociated to CO and H{sub 2} and 30% more energy obtained because waste heat is utilized. When one mol goes to three there is an expansion, and this is provided for. Both these designs result in clean fuelsmore » and are covered by U.S. patents.« less

Fermentation of D-xylose and L-arabinose to ethanol by Erwinia chrysanthemi

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tolan, J.S.; Finn, R.K.

1987-09-01

Erwinia spp. are gram-negative facultative anaerobes within the family Enterobacteriacae which possess several desirable traits for the conversion of pentose sugars to ethanol, such as the ability to ferment a broad range of carbohydrates and the ease with which they can be genetically modified. Twenty-eight strains of Erwinia carotovora and E. chrysanthemi were screened for the ability to ferment D-xylose to ethanol. E. chrysanthemi B374 was chosen for further study on the basis of its superior (4%) ethanol tolerance. They have characterized the fermentation of D-xylose and L-arabinose by the wild type and mutants which bear plasmids containing the pyruvatemore » decarboxylase gene from Zymomonas mobilis. Expression of the gene markedly increased the yields of ethanol (from 0.7 up to 1.45 mol/mol of xylose) and decreased the yields of formate, acetate, and lactate. However, the cells with pyruvate decarboxylase grew only one-fourth as fast as the wild type and tolerated only 2% ethanol. Alcohol tolerance was stimulated by the addition of yeast extract to the growth medium. Xylose catabolism was characterized by a high saturation constant K/sub s/ (4.5 mM).« less

Semicontinuous production of ethanol from agricultural wastes by immobilised coculture in a two stage bioreactor.

PubMed

Dey, Sabita

2002-10-01

The seed testing laboratories of Maharashtra discard 10 tonnes of grains and oil seeds treated with pesticides per annum. These agricultural wastes could be converted to reducing sugar and ethanol in a two stage semicontinuous fluidised bed bioreactor containing immobilised, Bacillus sp. and Zymomonas mobilis in the 1st stage and Saccharomyces diastaticus and S. cerevisae in the 2nd stage. The optimum temperature and pH for fermentation in both the stages were 30 degrees C and 7.2 respectively. In this process 600 g (approximately 400 g starch) waste seeds could yield 402 g of reducing sugar in the 1st stage after 20 h and 205 g ethanol in the 2nd stage after 40 h incubation with a yield factor 0.51. Using these system 10 tonnes of agricultural wastes could be converted to 3.4 x 107 g of ethanol.

Accounting for all sugars produced during integrated production of ethanol from lignocellulosic biomass

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schell, Daniel J.; Dowe, Nancy; Chapeaux, Alexandre

This study explored integrated conversion of corn stover to ethanol and highlights techniques for accurate yield calculations. Acid pretreated corn stover (PCS) produced in a pilot-scale reactor was enzymatically hydrolyzed and the resulting sugars were fermented to ethanol by the glucose–xylose fermenting bacteria, Zymomonas mobilis 8b. The calculations account for high solids operation and oligomeric sugars produced during pretreatment, enzymatic hydrolysis, and fermentation, which, if not accounted for, leads to overestimating ethanol yields. The calculations are illustrated for enzymatic hydrolysis and fermentation of PCS at 17.5% and 20.0% total solids achieving 80.1% and 77.9% conversion of cellulose and xylan tomore » ethanol and ethanol titers of 63 g/L and 69 g/L, respectively. In the future, these techniques, including the TEA results, will be applied to fully integrated pilot-scale runs.« less

Accounting for all sugars produced during integrated production of ethanol from lignocellulosic biomass

DOE PAGES

Schell, Daniel J.; Dowe, Nancy; Chapeaux, Alexandre; ...

2016-01-19

This study explored integrated conversion of corn stover to ethanol and highlights techniques for accurate yield calculations. Acid pretreated corn stover (PCS) produced in a pilot-scale reactor was enzymatically hydrolyzed and the resulting sugars were fermented to ethanol by the glucose–xylose fermenting bacteria, Zymomonas mobilis 8b. The calculations account for high solids operation and oligomeric sugars produced during pretreatment, enzymatic hydrolysis, and fermentation, which, if not accounted for, leads to overestimating ethanol yields. The calculations are illustrated for enzymatic hydrolysis and fermentation of PCS at 17.5% and 20.0% total solids achieving 80.1% and 77.9% conversion of cellulose and xylan tomore » ethanol and ethanol titers of 63 g/L and 69 g/L, respectively. In the future, these techniques, including the TEA results, will be applied to fully integrated pilot-scale runs.« less

Importance of stability study of continuous systems for ethanol production.

PubMed

Paz Astudillo, Isabel Cristina; Cardona Alzate, Carlos Ariel

2011-01-10

Fuel ethanol industry presents different problems during bioreactors operation. One of them is the unexpected variation in the output ethanol concentration from the bioreactor or a drastic fall in the productivity. In this paper, a compilation of concepts and relevant results of several experimental and theoretical studies about dynamic behavior of fermentation systems for bioethanol production with Saccharomyces cerevisiae and Zymomonas mobilis is done with the purpose of understanding the stability phenomena that could affect the productivity of industries producing fuel ethanol. It is shown that the design of high scale biochemical processes for fuel ethanol production must be done based on stability studies. © 2010 Elsevier B.V. All rights reserved.

Biosynthetic burden and plasmid burden limit expression of chromosomally integrated heterologous genes (pdc, adhB) in Escherichia coli

DOE Office of Scientific and Technical Information (OSTI.GOV)

Martinez, A.; York, S.W.; Yomano, L.P.

1999-10-01

Previous studies have shown an unexpectedly high nutrient requirement for efficient ethanol production by ethanologenic recombinants of Escherichia coli B such as LY01 which contain chromosomally integrated Zymomonas mobilis genes (pdc, adhB) encoding the ethanol pathway. The basis for this requirement has been identified as a media-dependent effect on the expression of the Z. mobilis genes rather than a nutritional limitation. Ethanol production was substantially increased without additional nutrients simply by increasing the level of pyruvate decarboxylase activity. This was accomplished by adding a multicopy plasmid containing pdc alone (but not adhB alone) to strain LY01, and by adding multicopymore » plasmids which express pdc and adhB from strong promoters. New strong promoters were isolated from random fragments of Z. mobilis DNA and characterized but were not used to construct integrated biocatalysts. These promoters contained regions resembling recognition sites for 3 different E. coli sigma factors: {sigma}{sup 70}, {sigma}{sup 38}, and {sigma}{sup 28}. The most effective plasmid-based promoters for fermentation were recognized by multiple sigma factors, expressed both pdc and adhB at high levels, and produced ethanol efficiently while allowing up to 80% reduction in complex nutrients as compared to LY01. The ability to utilize multiple sigma factors may be advantageous to maintain the high levels of PDC and ADH needed for efficient ethanol production throughout batch fermentation.« less

Comparing the fermentation performance of Escherichia coli KO11, Saccharomyces cerevisiae 424A(LNH-ST) and Zymomonas mobilis AX101 for cellulosic ethanol production

PubMed Central

2010-01-01

Background Fermentations using Escherichia coli KO11, Saccharomyces cerevisiae 424A(LNH-ST), and Zymomonas mobilis AX101 are compared side-by-side on corn steep liquor (CSL) media and the water extract and enzymatic hydrolysate from ammonia fiber expansion (AFEX)-pretreated corn stover. Results The three ethanologens are able produce ethanol from a CSL-supplemented co-fermentation at a metabolic yield, final concentration and rate greater than 0.42 g/g consumed sugars, 40 g/L and 0.7 g/L/h (0-48 h), respectively. Xylose-only fermentation of the tested ethanologenic bacteria are five to eight times faster than 424A(LNH-ST) in the CSL fermentation. All tested strains grow and co-ferment sugars at 15% w/v solids loading equivalent of ammonia fiber explosion (AFEX)-pretreated corn stover water extract. However, both KO11 and 424A(LNH-ST) exhibit higher growth robustness than AX101. In 18% w/w solids loading lignocellulosic hydrolysate from AFEX pretreatment, complete glucose fermentations can be achieved at a rate greater than 0.77 g/L/h. In contrast to results from fermentation in CSL, S. cerevisiae 424A(LNH-ST) consumed xylose at the greatest extent and rate in the hydrolysate compared to the bacteria tested. Conclusions Our results confirm that glucose fermentations among the tested strains are effective even at high solids loading (18% by weight). However, xylose consumption in the lignocellulosic hydrolysate is the major bottleneck affecting overall yield, titer or rate of the process. In comparison, Saccharomyces cerevisiae 424A(LNH-ST) is the most relevant strains for industrial production for its ability to ferment both glucose and xylose from undetoxified and unsupplemented hydrolysate from AFEX-pretreated corn stover at high yield. PMID:20507563

Accounting for all sugars produced during integrated production of ethanol from lignocellulosic biomass.

PubMed

Schell, Daniel J; Dowe, Nancy; Chapeaux, Alexandre; Nelson, Robert S; Jennings, Edward W

2016-04-01

Accurate mass balance and conversion data from integrated operation is needed to fully elucidate the economics of biofuel production processes. This study explored integrated conversion of corn stover to ethanol and highlights techniques for accurate yield calculations. Acid pretreated corn stover (PCS) produced in a pilot-scale reactor was enzymatically hydrolyzed and the resulting sugars were fermented to ethanol by the glucose-xylose fermenting bacteria, Zymomonas mobilis 8b. The calculations presented here account for high solids operation and oligomeric sugars produced during pretreatment, enzymatic hydrolysis, and fermentation, which, if not accounted for, leads to overestimating ethanol yields. The calculations are illustrated for enzymatic hydrolysis and fermentation of PCS at 17.5% and 20.0% total solids achieving 80.1% and 77.9% conversion of cellulose and xylan to ethanol and ethanol titers of 63g/L and 69g/L, respectively. These procedures will be employed in the future and the resulting information used for techno-economic analysis. Copyright © 2016 Elsevier Ltd. All rights reserved.

Production of C4 and C5 branched-chain alcohols by engineered Escherichia. coli.

PubMed

Chen, Xiaoyan; Xu, Jingliang; Yang, Liu; Yuan, Zhenhong; Xiao, Shiyuan; Zhang, Yu; Liang, Cuiyi; He, Minchao; Guo, Ying

2015-11-01

Higher alcohols, longer chain alcohols, contain more than 3 carbon atoms, showed close energy advantages as gasoline, and were considered as the next generation substitution for chemical fuels. Higher alcohol biosynthesis by native microorganisms mainly needs gene expression of heterologous keto acid decarboxylase and alcohol dehydrogenases. In the present study, branched-chain α-keto acid decarboxylase gene from Lactococcus lactis subsp. lactis CICC 6246 (Kivd) and alcohol dehydrogenases gene from Zymomonas mobilis CICC 41465 (AdhB) were transformed into Escherichia coli for higher alcohol production. SDS-PAGE results showed these two proteins were expressed in the recombinant strains. The resulting strain was incubated in LB medium at 37 °C in Erlenmeyer flasks and much more 3-methyl-1-butanol (104 mg/L) than isobutanol (24 mg/L) was produced. However, in 5 g/L glucose-containing medium, the production of two alcohols was similar, 156 and 161 mg/L for C4 (isobutanol) and C5 (3-methyl-1-butanol) alcohol, respectively. Effects of fermentation factors including temperature, glucose content, and α-keto acid on alcohol production were also investigated. The increase of glucose content and the adding of α-keto acids facilitated the production of C4 and C5 alcohols. The enzyme activities of pure Kivd on α-ketoisovalerate and α-ketoisocaproate were 26.77 and 21.24 μmol min(-1) mg(-1), respectively. Due to its ability on decarboxylation of α-ketoisovalerate and α-ketoisocaproate, the recombinant E. coli strain showed potential application on isoamyl alcohol and isobutanol production.

Inhibition of microbial biofuel production in drought-stressed switchgrass hydrolysate

DOE PAGES

Ong, Rebecca Garlock; Higbee, Alan; Bottoms, Scott; ...

2016-11-08

Here, interannual variability in precipitation, particularly drought, can affect lignocellulosic crop biomass yields and composition, and is expected to increase biofuel yield variability. However, the effect of precipitation on downstream fermentation processes has never been directly characterized. In order to investigate the impact of interannual climate variability on biofuel production, corn stover and switchgrass were collected during 3 years with significantly different precipitation profiles, representing a major drought year (2012) and 2 years with average precipitation for the entire season (2010 and 2013). All feedstocks were AFEX (ammonia fiber expansion)-pretreated, enzymatically hydrolyzed, and the hydrolysates separately fermented using xylose-utilizing strainsmore » of Saccharomyces cerevisiae and Zymomonas mobilis. As a result, a chemical genomics approach was also used to evaluate the growth of yeast mutants in the hydrolysates.« less

Shear bond strengths of an indirect composite layering material to a tribochemically silica-coated zirconia framework material.

PubMed

Iwasaki, Taro; Komine, Futoshi; Fushiki, Ryosuke; Kubochi, Kei; Shinohara, Mitsuyo; Matsumura, Hideo

2016-01-01

This study evaluated shear bond strengths of a layering indirect composite material to a zirconia framework material treated with tribochemical silica coating. Zirconia disks were divided into two groups: ZR-PRE (airborne-particle abrasion) and ZR-PLU (tribochemical silica coating). Indirect composite was bonded to zirconia treated with one of the following primers: Clearfil Ceramic Primer (CCP), Clearfil Mega Bond Primer with Clearfil Porcelain Bond Activator (MGP+Act), ESPE-Sil (SIL), Estenia Opaque Primer, MR. Bond, Super-Bond PZ Primer Liquid A with Liquid B (PZA+PZB), and Super-Bond PZ Primer Liquid B (PZB), or no treatment. Shear bond testing was performed at 0 and 20,000 thermocycles. Post-thermocycling shear bond strengths of ZR-PLU were higher than those of ZR-PRE in CCP, MGP+Act, SIL, PZA+PZB, and PZB groups. Application of silane yielded better durable bond strengths of a layering indirect composite material to a tribochemically silica-coated zirconia framework material.

Genetic engineering of Clostridium thermocellum DSM1313 for enhanced ethanol production.

PubMed

Kannuchamy, Saranyah; Mukund, Nisha; Saleena, Lilly M

2016-05-11

The twin problem of shortage in fossil fuel and increase in environmental pollution can be partly addressed by blending of ethanol with transport fuel. Increasing the ethanol production for this purpose without affecting the food security of the countries would require the use of cellulosic plant materials as substrate. Clostridium thermocellum is an anaerobic thermophilic bacterium with cellulolytic property and the ability to produce ethanol. But its application as biocatalyst for ethanol production is limited because pyruvate ferredoxin oxidoreductase, which diverts pyruvate to ethanol production pathway, has low affinity to the substrate. Therefore, the present study was undertaken to genetically modify C. thermocellum for enhancing its ethanol production capacity by transferring pyruvate carboxylase (pdc) and alcohol dehydrogenase (adh) genes of the homoethanol pathway from Zymomonas mobilis. The pdc and adh genes from Z. mobilis were cloned in pNW33N, and transformed to Clostridium thermocellum DSM 1313 by electroporation to generate recombinant CTH-pdc, CTH-adh and CTH-pdc-adh strains that carried heterologous pdc, adh, and both genes, respectively. The plasmids were stably maintained in the recombinant strains. Though both pdc and adh were functional in C. thermocellum, the presence of adh severely limited the growth of the recombinant strains, irrespective of the presence or absence of the pdc gene. The recombinant CTH-pdc strain showed two-fold increase in pyruvate carboxylase activity and ethanol production when compared with the wild type strain. Pyruvate decarboxylase gene of the homoethanol pathway from Z mobilis was functional in recombinant C. thermocellum strain and enhanced its ability to produced ethanol. Strain improvement and bioprocess optimizations may further increase the ethanol production from this recombinant strain.

OptSSeq: High-throughput sequencing readout of growth enrichment defines optimal gene expression elements for homoethanologenesis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ghosh, Indro Neil; Landick, Robert

The optimization of synthetic pathways is a central challenge in metabolic engineering. OptSSeq (Optimization by Selection and Sequencing) is one approach to this challenge. OptSSeq couples selection of optimal enzyme expression levels linked to cell growth rate with high-throughput sequencing to track enrichment of gene expression elements (promoters and ribosomebinding sites) from a combinatorial library. OptSSeq yields information on both optimal and suboptimal enzyme levels, and helps identify constraints that limit maximal product formation. Here we report a proof-of-concept implementation of OptSSeq using homoethanologenesis, a two-step pathway consisting of pyruvate decarboxylase (Pdc) and alcohol dehydrogenase (Adh) that converts pyruvate tomore » ethanol and is naturally optimized in the bacterium Zymomonas mobilis. We used OptSSeq to determine optimal gene expression elements and enzyme levels for Z. mobilis Pdc, AdhA, and AdhB expressed in Escherichia coli. By varying both expression signals and gene order, we identified an optimal solution using only Pdc and AdhB. We resolved current uncertainty about the functions of the Fe 2+-dependent AdhB and Zn 2+- dependent AdhA by showing that AdhB is preferred over AdhA for rapid growth in both E. coli and Z. mobilis. Finally, by comparing predictions of growth-linked metabolic flux to enzyme synthesis costs, we established that optimal E. coli homoethanologenesis was achieved by our best pdc-adhB expression cassette and that the remaining constraints lie in the E. coli metabolic network or inefficient Pdc or AdhB function in E. coli. Furthermore, OptSSeq is a general tool for synthetic biology to tune enzyme levels in any pathway whose optimal function can be linked to cell growth or survival.« less

OptSSeq: High-throughput sequencing readout of growth enrichment defines optimal gene expression elements for homoethanologenesis

DOE PAGES

Ghosh, Indro Neil; Landick, Robert

2016-07-16

The optimization of synthetic pathways is a central challenge in metabolic engineering. OptSSeq (Optimization by Selection and Sequencing) is one approach to this challenge. OptSSeq couples selection of optimal enzyme expression levels linked to cell growth rate with high-throughput sequencing to track enrichment of gene expression elements (promoters and ribosomebinding sites) from a combinatorial library. OptSSeq yields information on both optimal and suboptimal enzyme levels, and helps identify constraints that limit maximal product formation. Here we report a proof-of-concept implementation of OptSSeq using homoethanologenesis, a two-step pathway consisting of pyruvate decarboxylase (Pdc) and alcohol dehydrogenase (Adh) that converts pyruvate tomore » ethanol and is naturally optimized in the bacterium Zymomonas mobilis. We used OptSSeq to determine optimal gene expression elements and enzyme levels for Z. mobilis Pdc, AdhA, and AdhB expressed in Escherichia coli. By varying both expression signals and gene order, we identified an optimal solution using only Pdc and AdhB. We resolved current uncertainty about the functions of the Fe 2+-dependent AdhB and Zn 2+- dependent AdhA by showing that AdhB is preferred over AdhA for rapid growth in both E. coli and Z. mobilis. Finally, by comparing predictions of growth-linked metabolic flux to enzyme synthesis costs, we established that optimal E. coli homoethanologenesis was achieved by our best pdc-adhB expression cassette and that the remaining constraints lie in the E. coli metabolic network or inefficient Pdc or AdhB function in E. coli. Furthermore, OptSSeq is a general tool for synthetic biology to tune enzyme levels in any pathway whose optimal function can be linked to cell growth or survival.« less

Sucrose dependent mineral phosphate solubilization in Enterobacter asburiae PSI3 by heterologous overexpression of periplasmic invertases.

PubMed

Kumar, Chanchal; Wagh, Jitendra; Archana, G; Naresh Kumar, G

2016-12-01

Enterobacter asburiae PSI3 solubilizes mineral phosphates in the presence of glucose by the secretion of gluconic acid generated by the action of a periplasmic pyrroloquinoline quinone dependent glucose dehydrogenase. In order to achieve mineral phosphate solubilization phenotype in the presence of sucrose, plasmids pCNK4 and pCNK5 containing genes encoding the invertase enzyme of Zymomonas mobilis (invB) and of Saccharomyces cerevisiae (suc2) under constitutive promoters were constructed with malE signal sequence (in case of invB alone as the suc2 is secreted natively). When introduced into E. asburiae PSI3, E. a. (pCNK4) and E. a. (pCNK5) transformants secreted 21.65 ± 0.94 and 22 ± 1.3 mM gluconic acid, respectively, in the presence of 75 mM sucrose and they also solubilized 180 ± 4.3 and 438 ± 7.3 µM P from the rock phosphate. In the presence of a mixture of 50 mM sucrose and 25 mM glucose, E. a. (pCNK5) secreted 34 ± 2.3 mM gluconic acid and released 479 ± 8.1 µM P. Moreover, in the presence of a mixture of eight sugars (10 mM each) in the medium, E. a. (pCNK5) released 414 ± 5.3 µM P in the buffered medium. Thus, this study demonstrates incorporation of periplasmic invertase imparted P solubilization ability to E. asburiae PSI3 in the presence of sucrose and mixture of sugars.

Recombinant cells that highly express chromosomally-integrated heterologous genes

DOEpatents

Ingram, L.O.; Ohta, Kazuyoshi; Wood, B.E.

1998-10-13

Recombinant host cells are obtained that comprise (A) a heterologous, polypeptide-encoding polynucleotide segment, stably integrated into a chromosome, which is under transcriptional control of an endogenous promoter and (B) a mutation that effects increased expression of the heterologous segment, resulting in enhanced production by the host cells of each polypeptide encoded by that segment, relative to production of each polypeptide by the host cells in the absence of the mutation. The increased expression thus achieved is retained in the absence of conditions that select for cells displaying such increased expression. When the integrated segment comprises, for example, ethanol-production genes from an efficient ethanol producer like Zymomonas mobilis, recombinant Escherichia coli and other enteric bacterial cells within the present invention are capable of converting a wide range of biomass-derived sugars efficiently to ethanol. 13 figs.

Recombinant cells that highly express chromosomally-integrated heterologous genes

DOEpatents

Ingram, Lonnie O.; Ohta, Kazuyoshi; Wood, Brent E.

1998-01-01

Recombinant host cells are obtained that comprise (A) a heterologous, polypeptide-encoding polynucleotide segment, stably integrated into a chromosome, which is under transcriptional control of an endogenous promoter and (B) a mutation that effects increased expression of the heterologous segment, resulting in enhanced production by the host cells of each polypeptide encoded by that segment, relative to production of each polypeptide by the host cells in the absence of the mutation. The increased expression thus achieved is retained in the absence of conditions that select for cells displaying such increased expression. When the integrated segment comprises, for example, ethanol-production genes from an efficient ethanol producer like Zymomonas mobilis, recombinant Escherichia coli and other enteric bacterial cells within the present invention are capable of converting a wide range of biomass-derived sugars efficiently to ethanol.

Recombinant cells that highly express chromosomally-integrated heterologous gene

DOEpatents

Ingram, Lonnie O.; Ohta, Kazuyoshi; Wood, Brent E.

2007-03-20

Recombinant host cells are obtained that comprise (A) a heterologous, polypeptide-encoding polynucleotide segment, stably integrated into a chromosome, which is under transcriptional control of an endogenous promoter and (B) a mutation that effects increased expression of the heterologous segment, resulting in enhanced production by the host cells of each polypeptide encoded by that segment, relative to production of each polypeptide by the host cells in the absence of the mutation. The increased expression thus achieved is retained in the absence of conditions that select for cells displaying such increased expression. When the integrated segment comprises, for example, ethanol-production genes from an efficient ethanol producer like Zymomonas mobilis, recombinant Escherichia coli and other enteric bacterial cells within the present invention are capable of converting a wide range of biomass-derived sugars efficiently to ethanol.

Recombinant cells that highly express chromosomally-integrated heterologous genes

DOEpatents

Ingram, Lonnie O.; Ohta, Kazuyoshi; Wood, Brent E.

2000-08-22

Recombinant host cells are obtained that comprise (A) a heterologous, polypeptide-encoding polynucleotide segment, stably integrated into a chromosome, which is under transcriptional control of an endogenous promoter and (B) a mutation that effects increased expression of the heterologous segment, resulting in enhanced production by the host cells of each polypeptide encoded by that segment, relative to production of each polypeptide by the host cells in the absence of the mutation. The increased expression thus achieved is retained in the absence of conditions that select for cells displaying such increased expression. When the integrated segment comprises, for example, ethanol-production genes from an efficient ethanol producer like Zymomonas mobilis, recombinant Escherichia coli and other enteric bacterial cells within the present invention are capable of converting a wide range of biomass-derived sugars efficiently to ethanol.

Bioethanol production by heterologous expression of Pdc and AdhII in Streptomyces lividans.

PubMed

Lee, Jae Sun; Chi, Won-Jae; Hong, Soon-Kwang; Yang, Ji-Won; Chang, Yong Keun

2013-07-01

Two genes from Zymomonas mobilis that are responsible for ethanol production, pyruvate decarboxylase (pdc) and alcohol dehydrogenase II (adhII), were heterologously expressed in the Gram-positive bacterium Streptomyces lividans TK24. An examination of carbon distribution revealed that a significant portion of carbon metabolism was switched from biomass and organic acid biosynthesis to ethanol production upon the expression of pdc and adhII. The recombinant S. lividans TK24 produced ethanol from glucose with a yield of 23.7% based on the carbohydrate consumed. The recombinant was able to produce ethanol from xylose, L-arabinose, mannose, L-rhamnose, galactose, ribose, and cellobiose with yields of 16.0, 25.6, 21.5, 33.6, 30.6, 14.6, and 33.3%, respectively. Polymeric substances such as starch and xylan were directly converted to ethanol by the recombinant with ethanol yields of 18.9 and 8.8%, respectively. The recombinant S. lividans TK24/Tpet developed in this study is potentially a useful microbial resource for ethanol production from various sources of biomasses, especially microalgae.

Enhancement of expression and apparent secretion of Erwinia chrysanthemi endoglucanase (encoded by celZ) in Escherichia coli B

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhou, S.; Yomano, L.P.; Saleh, A.Z.

1999-06-01

Escherichia coli B has been engineered as a biocatalyst for the conversion of lignocellulose into ethanol. Previous research has demonstrated that derivatives of E. coli B can produce high levels of Erwinia chrysanthemi endoglucanase (encoded by celZ) as a periplasmic product and that this enzyme can function with commercial fungal cellulase to increase ethanol production. In this study, the authors have demonstrated two methods that improve celZ expression in E. coli B. Initially, with a low-copy-number vector, two E. coli glycolytic gene promoters (gap and eno) were tested and found to be less effective than the original celZ promoter. Bymore » screening 18,000 random fragments of Zymomonas mobilis DNA, a surrogate promoter was identified which increased celZ expression up to sixfold. With this promoter, large polar inclusion bodies were clearly evident in the periplasmic space. Sequencing revealed that the most active surrogate promoter is derived from five Sau3A1 fragments, one of which was previously sequenced in Z. mobilis. Visual inspection indicated that this DNA fragment contains at least five putative promoter regions, two of which were confirmed by primer extension analysis. Addition of the out genes from E. chrysanthemi EC16 caused a further increase in the production of active enzyme and facilitated secretion or release of over half of the activity into the extracellular environment. With the most active construct, of a total of 13,000 IU of active enzyme per liter of culture, 7,800 IU was in the supernatant. The total active endoglucanase was estimated to represent 4 to 6% of cellular protein.« less

Mathematical modeling of ethanol production in solid-state fermentation based on solid medium' dry weight variation.

PubMed

Mazaheri, Davood; Shojaosadati, Seyed Abbas; Zamir, Seyed Morteza; Mousavi, Seyyed Mohammad

2018-04-21

In this work, mathematical modeling of ethanol production in solid-state fermentation (SSF) has been done based on the variation in the dry weight of solid medium. This method was previously used for mathematical modeling of enzyme production; however, the model should be modified to predict the production of a volatile compound like ethanol. The experimental results of bioethanol production from the mixture of carob pods and wheat bran by Zymomonas mobilis in SSF were used for the model validation. Exponential and logistic kinetic models were used for modeling the growth of microorganism. In both cases, the model predictions matched well with the experimental results during the exponential growth phase, indicating the good ability of solid medium weight variation method for modeling a volatile product formation in solid-state fermentation. In addition, using logistic model, better predictions were obtained.

[Optimization of fuel ethanol production from kitchen waste by Plackett-Burman design].

PubMed

Ma, Hong-Zhi; Gong, Li-Juan; Wang, Qun-Hui; Zhang, Wen-Yu; Xu, Wen-Long

2008-05-01

Kitchen garbage was chosen to produce ethanol through simultaneous saccharification and fermentation (SSF) by Zymomonas mobilis. Plackett-Burman design was employed to screen affecting parameters during SSF process. The parameters were divided into two parts, enzymes and nutritions. None of the nutritions added showed significant effect during the experiment, which demonstrated that the kitchen garbage could meet the requirement of the microorganism without extra supplementation. Protease and glucoamylase were determined to be affecting factors for ethanol production. Single factor experiment showed that the optimum usage of these two enzymes were both 100 U/g and the corresponding maximum ethanol was determined to be 53 g/L. The ethanol yield could be as high as 44%. The utilization of kitchen garbage to produce ethanol could reduce threaten of waste as well as improve the protein content of the spent. This method could save the ethanol production cost and benefit for the recycle of kitchen garbage.

Classification of Rhizomonas suberifaciens, an unnamed Rhizomonas species, and Sphingomonas spp. in rRNA superfamily IV.

PubMed

van Bruggen, A H; Jochimsen, K N; Steinberger, E M; Segers, P; Gillis, M

1993-01-01

Thermal melting profiles of hybrids between 3H-labeled rRNA of Rhizomonas suberifaciens, the causal agent of corky root of lettuce, and chromosomal DNAs from 27 species of gram-negative bacteria indicated that the genus Rhizomonas belongs to superfamily IV of De Ley. On the basis of the melting temperatures of DNA hybrids with rRNAs from the type strains of R. suberifaciens, Sphingomonas paucimobilis, and Sphingomonas capsulata, Rhizomonas strains constitute a separate branch in superfamily IV, which is closely related to but separate from branches containing Zymomonas mobilis, Sphingomonas spp., and S. capsulata. Sphingomonas yanoikuyae and Rhizomonas sp. strain WI4 are located toward the base of the Rhizomonas rRNA branch. DNA-DNA hybridization indicated that S. yanoikuyae is equidistant from Rhizomonas sp. strain WI4 and S. paucimobilis. Sequences of 270 bp of 16S ribosomal DNAs from eight strains of Rhizomonas spp., eight strains of Sphingomonas spp., and Agrobacterium tumefaciens indicated that S. yanoikuyae and Rhizomonas sp. strains WI4 and CA16 are genetically more closely related to R. suberifaciens than to Sphingomonas spp. Thus, S. yanoikuyae may need to be transferred to the genus Rhizomonas on the basis of the results of further study.

Technique of ethanol food grade production with batch distillation and dehydration using starch-based adsorbent

NASA Astrophysics Data System (ADS)

Widjaja, Tri; Altway, Ali; Ni'mah, Hikmatun; Tedji, Namira; Rofiqah, Umi

2015-12-01

Development and innovation of ethanol food grade production are becoming the reasearch priority to increase economy growth. Moreover, the government of Indonesia has established regulation for increasing the renewable energy as primary energy. Sorghum is cerealia plant that contains 11-16% sugar that is optimum for fermentation process, it is potential to be cultivated, especially at barren area in Indonesia. The purpose of this experiment is to learn about the effect of microorganisms in fermentation process. Fermentation process was carried out batchwise in bioreactor and used 150g/L initial sugar concentration. Microorganisms used in this experiment are Zymomonas mobilis mutation (A3), Saccharomyces cerevisiae and mixed of Pichia stipitis. The yield of ethanol can be obtained from this experiment. For ethanol purification result, distillation process from fermentation process has been done to search the best operation condition for efficiency energy consumption. The experiment for purification was divided into two parts, which are distillation with structured packing steel wool and adsorption (dehydration) sequencely. In distillation part, parameters evaluation (HETP and pressure drop) of distillation column that can be used for scale up are needed. The experiment was operated at pressure of 1 atm. The distillation stage was carried out at 85 °C and reflux ratio of 0.92 with variety porosities of 20%, 40%, and 60%. Then the adsorption process was done at 120°C and two types of adsorbent, which are starch - based adsorbent with ingredient of cassava and molecular sieve 3A, were used. The adsorption process was then continued to purify the ethanol from impurities by using activated carbon. This research shows that the batch fermentation process with Zymomonas mobilis A3 obtain higher % yield of ethanol of 40,92%. In addition to that, for purification process, the best operation condition is by using 40% of porosity of stuctured packing steel wool in distillation stage and starch-based adsorbent in adsorption stage, which can obtain ethanol content of 92,15% with acetic acid percentage of 0,001% and the rest is water. This result is qualified for ethanol food grade specification which is between 90 - 94 % of ethanol with maximum percentage of acetic acid is 0,003%, and passes in fusel oil and isopropyl alcohol test.

Bacterial supersystem for alginate import/metabolism and its environmental and bioenergy applications.

PubMed

Hashimoto, Wataru; Kawai, Shigeyuki; Murata, Kousaku

2010-01-01

Distinct from most alginate-assimilating bacteria that secrete polysaccharide lyases extracellularly, a gram-negative bacterium, Sphingomonas sp. A1 (strain A1), can directly incorporate alginate into its cytoplasm, without degradation, through a "superchannel" consisting of a mouth-like pit on the cell surface, periplasmic binding proteins, and a cytoplasmic membrane-bound ATP-binding cassette transporter. Flagellin homologues function as cell surface alginate receptors essential for expressing the superchannel. Cytoplasmic alginate lyases with different substrate specificities and action modes degrade the polysaccharide to its constituent monosaccharides. The resultant monosaccharides, α-keto acids, are converted to a reduced form by NADPH-dependent reductase, and are finally metabolized in the TCA cycle. Transplantation of the strain A1 superchannel to xenobiotic-degrading sphingomonads enhances bioremediation through the propagation of bacteria with an elevated transport activity. Furthermore, strain A1 cells transformed with Zymomonas mobilis genes for pyruvate decarboxylase and alcohol dehydrogenase II produce considerable amounts of biofuel ethanol from alginate when grown statically. © 2010 Landes Bioscience

Metabolically engineered glucose-utilizing Shewanella strains under anaerobic conditions.

PubMed

Choi, Donggeon; Lee, Sae Bom; Kim, Sohyun; Min, Byoungnam; Choi, In-Geol; Chang, In Seop

2014-02-01

Comparative genome analysis of Shewanella strains predicted that the strains metabolize preferably two- and three-carbon carbohydrates as carbon/electron source because many Shewanella genomes are deficient of the key enzymes in glycolysis (e.g., glucokinase). In addition, all Shewanella genomes are known to have only one set of genes associated with the phosphotransferase system required to uptake sugars. To engineer Shewanella strains that can utilize five- and six-carbon carbohydrates, we constructed glucose-utilizing Shewanella oneidensis MR-1 by introducing the glucose facilitator (glf; ZMO0366) and glucokinase (glk; ZMO0369) genes of Zymomonas mobilis. The engineered MR-1 strain was able to grow on glucose as a sole carbon/electron source under anaerobic conditions. The glucose affinity (Ks) and glucokinase activity in the engineered MR-1 strain were 299.46 mM and 0.259 ± 0.034 U/g proteins. The engineered strain was successfully applied to a microbial fuel cell system and exhibited current generation using glucose as the electron source. Copyright © 2013 Elsevier Ltd. All rights reserved.

Single-species microbial biofilm screening for industrial applications.

PubMed

Li, Xuan Zhong; Hauer, Bernhard; Rosche, Bettina

2007-10-01

While natural microbial biofilms often consist of multiple species, single-species biofilms are of great interest to biotechnology. The current study evaluates biofilm formation for common industrial and laboratory microorganisms. A total of 68 species of biosafety level one bacteria and yeasts from over 40 different genera and five phyla were screened by growing them in microtiter plates and estimating attached biomass by crystal violet staining. Most organisms showed biofilm formation on surfaces of polystyrene within 24 h. By changing a few simple conditions such as substratum characteristics, inoculum and nutrient availability, 66 strains (97%) demonstrated biofilm formation under at least one of the experimental conditions and over half of these strains were classified as strong biofilm formers, potentially suitable as catalysts in biofilm applications. Many non-motile bacteria were also strong biofilm formers. Biofilm morphologies were visualized for selected strains. A model organism, Zymomonas mobilis, easily established itself as a biofilm on various reactor packing materials, including stainless steel.

Simultaneous consumption of pentose and hexose sugars: an optimal microbial phenotype for efficient fermentation of lignocellulosic biomass.

PubMed

Kim, Jae-Han; Block, David E; Mills, David A

2010-11-01

Lignocellulosic biomass is an attractive carbon source for bio-based fuel and chemical production; however, its compositional heterogeneity hinders its commercial use. Since most microbes possess carbon catabolite repression (CCR), mixed sugars derived from the lignocellulose are consumed sequentially, reducing the efficacy of the overall process. To overcome this barrier, microbes that exhibit the simultaneous consumption of mixed sugars have been isolated and/or developed and evaluated for the lignocellulosic biomass utilization. Specific strains of Escherichia coli, Saccharomyces cerevisiae, and Zymomonas mobilis have been engineered for simultaneous glucose and xylose utilization via mutagenesis or introduction of a xylose metabolic pathway. Other microbes, such as Lactobacillus brevis, Lactobacillus buchneri, and Candida shehatae possess a relaxed CCR mechanism, showing simultaneous consumption of glucose and xylose. By exploiting CCR-negative phenotypes, various integrated processes have been developed that incorporate both enzyme hydrolysis of lignocellulosic material and mixed sugar fermentation, thereby enabling greater productivity and fermentation efficacy.

Conceptual design of cost-effective and environmentally-friendly configurations for fuel ethanol production from sugarcane by knowledge-based process synthesis.

PubMed

Sánchez, Óscar J; Cardona, Carlos A

2012-01-01

In this work, the hierarchical decomposition methodology was used to conceptually design the production of fuel ethanol from sugarcane. The decomposition of the process into six levels of analysis was carried out. Several options of technological configurations were assessed in each level considering economic and environmental criteria. The most promising alternatives were chosen rejecting the ones with a least favorable performance. Aspen Plus was employed for simulation of each one of the technological configurations studied. Aspen Icarus was used for economic evaluation of each configuration, and WAR algorithm was utilized for calculation of the environmental criterion. The results obtained showed that the most suitable synthesized flowsheet involves the continuous cultivation of Zymomonas mobilis with cane juice as substrate and including cell recycling and the ethanol dehydration by molecular sieves. The proposed strategy demonstrated to be a powerful tool for conceptual design of biotechnological processes considering both techno-economic and environmental indicators. Copyright © 2011 Elsevier Ltd. All rights reserved.

Simultaneous consumption of pentose and hexose sugars: an optimal microbial phenotype for efficient fermentation of lignocellulosic biomass

PubMed Central

Kim, Jae-Han; Block, David E.

2010-01-01

Lignocellulosic biomass is an attractive carbon source for bio-based fuel and chemical production; however, its compositional heterogeneity hinders its commercial use. Since most microbes possess carbon catabolite repression (CCR), mixed sugars derived from the lignocellulose are consumed sequentially, reducing the efficacy of the overall process. To overcome this barrier, microbes that exhibit the simultaneous consumption of mixed sugars have been isolated and/or developed and evaluated for the lignocellulosic biomass utilization. Specific strains of Escherichia coli, Saccharomyces cerevisiae, and Zymomonas mobilis have been engineered for simultaneous glucose and xylose utilization via mutagenesis or introduction of a xylose metabolic pathway. Other microbes, such as Lactobacillus brevis, Lactobacillus buchneri, and Candida shehatae possess a relaxed CCR mechanism, showing simultaneous consumption of glucose and xylose. By exploiting CCR-negative phenotypes, various integrated processes have been developed that incorporate both enzyme hydrolysis of lignocellulosic material and mixed sugar fermentation, thereby enabling greater productivity and fermentation efficacy. PMID:20838789

Three immobilized-cell columnar bioreactors for enhanced production of commodity chemicals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Davison, B.H.; Scott, C.D.; Kaufman, E.N.

1993-12-31

Immobilized-cell fluidized-bed bioreactors (FBRs) can be used with a variety of fermentations to increase production of fuels, solvents, organic acids, and other fermentation products. Part of the increased rates and yields are due to the immobilization of the biocatalyst at high concentrations. This FBR system with immobilized Zymomonas mobilis increased ethanol productivity more than tenfold with 99% conversion and near stoichiometric yields. FBRs also offer several additional modes of operation for simultaneous fermentation and separation to further increase production by removing the inhibitory products directly from the continuous fermentation. The production of lactic acid by immobilized Lactobacillus was augmented withmore » the addition and removal of solid adsorbent particles to the FBR. An immiscible organic extractant also was used to extract butanol from the acetone-butanol fermentation by Clostridium acetobutylicum. Demonstrations with these FBR systems have already shown definite advantages by improved overall product yields (decreasing feed costs) and by increased rates (decreasing capital and operating costs). Further demonstration and scale-up continue.« less

Bioethanol production from fermentable sugar juice.

PubMed

Zabed, Hossain; Faruq, Golam; Sahu, Jaya Narayan; Azirun, Mohd Sofian; Hashim, Rosli; Boyce, Amru Nasrulhaq

2014-01-01

Bioethanol production from renewable sources to be used in transportation is now an increasing demand worldwide due to continuous depletion of fossil fuels, economic and political crises, and growing concern on environmental safety. Mainly, three types of raw materials, that is, sugar juice, starchy crops, and lignocellulosic materials, are being used for this purpose. This paper will investigate ethanol production from free sugar containing juices obtained from some energy crops such as sugarcane, sugar beet, and sweet sorghum that are the most attractive choice because of their cost-effectiveness and feasibility to use. Three types of fermentation process (batch, fed-batch, and continuous) are employed in ethanol production from these sugar juices. The most common microorganism used in fermentation from its history is the yeast, especially, Saccharomyces cerevisiae, though the bacterial species Zymomonas mobilis is also potentially used nowadays for this purpose. A number of factors related to the fermentation greatly influences the process and their optimization is the key point for efficient ethanol production from these feedstocks.

De novo Biosynthesis of Biodiesel by Escherichia coli in Optimized Fed-Batch Cultivation

PubMed Central

Cai, Ke; Tan, Xiaoming; Lu, Xuefeng

2011-01-01

Biodiesel is a renewable alternative to petroleum diesel fuel that can contribute to carbon dioxide emission reduction and energy supply. Biodiesel is composed of fatty acid alkyl esters, including fatty acid methyl esters (FAMEs) and fatty acid ethyl esters (FAEEs), and is currently produced through the transesterification reaction of methanol (or ethanol) and triacylglycerols (TAGs). TAGs are mainly obtained from oilseed plants and microalgae. A sustainable supply of TAGs is a major bottleneck for current biodiesel production. Here we report the de novo biosynthesis of FAEEs from glucose, which can be derived from lignocellulosic biomass, in genetically engineered Escherichia coli by introduction of the ethanol-producing pathway from Zymomonas mobilis, genetic manipulation to increase the pool of fatty acyl-CoA, and heterologous expression of acyl-coenzyme A: diacylglycerol acyltransferase from Acinetobacter baylyi. An optimized fed-batch microbial fermentation of the modified E. coli strain yielded a titer of 922 mg L−1 FAEEs that consisted primarily of ethyl palmitate, -oleate, -myristate and -palmitoleate. PMID:21629774

Bioethanol Production from Fermentable Sugar Juice

PubMed Central

Zabed, Hossain; Faruq, Golam; Sahu, Jaya Narayan; Azirun, Mohd Sofian; Hashim, Rosli; Nasrulhaq Boyce, Amru

2014-01-01

Bioethanol production from renewable sources to be used in transportation is now an increasing demand worldwide due to continuous depletion of fossil fuels, economic and political crises, and growing concern on environmental safety. Mainly, three types of raw materials, that is, sugar juice, starchy crops, and lignocellulosic materials, are being used for this purpose. This paper will investigate ethanol production from free sugar containing juices obtained from some energy crops such as sugarcane, sugar beet, and sweet sorghum that are the most attractive choice because of their cost-effectiveness and feasibility to use. Three types of fermentation process (batch, fed-batch, and continuous) are employed in ethanol production from these sugar juices. The most common microorganism used in fermentation from its history is the yeast, especially, Saccharomyces cerevisiae, though the bacterial species Zymomonas mobilis is also potentially used nowadays for this purpose. A number of factors related to the fermentation greatly influences the process and their optimization is the key point for efficient ethanol production from these feedstocks. PMID:24715820

Simultaneous saccharification of inulin and starch using commercial glucoamylase and the subsequent bioconversion to high titer sorbitol and gluconic acid.

PubMed

An, Kehong; Hu, Fengxian; Bao, Jie

2013-12-01

A new bioprocess for production of sorbitol and gluconic acid from two low-cost feedstocks, inulin and cassava starch, using a commercially available enzyme was proposed in this study. The commercial glucoamylase GA-L NEW from Genencor was found to demonstrate a high inulinase activity for hydrolysis of inulin into fructose and glucose. The glucoamylase was used to replace the expensive and not commercially available inulinase enzyme for simultaneous saccharification of inulin and starch into high titer glucose and fructose hydrolysate. The glucose and fructose in the hydrolysate were converted into sorbitol and gluconic acid using immobilized whole cells of the recombinant Zymomonas mobilis strain. The high gluconic acid concentration of 193 g/L and sorbitol concentration of 180 g/L with the overall yield of 97.3 % were obtained in the batch operations. The present study provided a practical production method of sorbitol and gluconic acid from low cost feedstocks and enzymes.

Fermentation of xylose to ethanol by genetically modified enteric bacteria

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tolan, J.S.

1987-01-01

This thesis describes the fermentation of D-xylose by wild type and recombinant Klebsiella planticola ATCC 33531 and Erwinia chrysanthemi B374. The recombinant strains bear multi-copy plasmids containing the pdc gene inserted from Zymomonas mobilis. Expression of the gene in K. planticola markedly increased the yield of ethanol, up to 1.3 mole/mole xylose, or 25.1 g/L. Concurrently, there were significant decreases in the yields of formation acetate, lactate, and butanediol. Transconjugant Klebsiella grew almost as fast as the wild type and tolerated up to 4% ethanol. The plasmid was retained by the cells during at least one batch culture, even inmore » the absence of selective pressure by antibiotics to maintain the plasmid. The cells produced 31.6 g/L ethanol from 79.6 g/L of a D-glucose-D-xylose-L-arabinose mixture designed to simulate hydrolyzed hemicellulose. The physiology of the wild type K. planticola is described in more detail than in the original report of its isolation. E. chrysanthemi PDC transconjugants also produced ethanol in high yield (up to 1.45 mole/mole xylose). However, transconjugant E. chrysanthemi grew only 1/4 as rapidly as the wild type and tolerated only 2% ethanol. The plasmid PZM15 apparently exhibits pleiotropic effects when inserted into K. planticola and into E. chrysanthemi.« less

Synthesis and biological activity of lipophilic analogs of the cationic antimicrobial active peptide anoplin.

PubMed

Chionis, Kostas; Krikorian, Dimitrios; Koukkou, Anna-Irini; Sakarellos-Daitsiotis, Maria; Panou-Pomonis, Eugenia

2016-11-01

Anoplin is a short natural cationic antimicrobial peptide which is derived from the venom sac of the solitary wasp, Anoplius samariensis. Due to its short sequence G 1 LLKR 5 IKT 8 LL-NH 2 , it is ideal for research tests. In this study, novel analogs of anoplin were prepared and examined for their antimicrobial, hemolytic activity, and proteolytic stability. Specific substitutions were introduced in amino acids Gly 1 , Arg 5 , and Thr 8 and lipophilic groups with different lengths in the N-terminus in order to investigate how these modifications affect their antimicrobial activity. These cationic analogs exhibited higher antimicrobial activity than the native peptide; they are also nontoxic at their minimum inhibitory concentration (MIC) values and resistant to enzymatic degradation. The substituted peptide GLLKF 5 IKK 8 LL-NH 2 exhibited high activity against Gram-negative bacterium Zymomonas mobilis (MIC = 7 µg/ml), and the insertion of octanoic, decanoic, and dodecanoic acid residues in its N-terminus increased the antimicrobial activity against Gram-positive and Gram-negative bacteria (MIC = 5 µg/ml). The conformational characteristics of the peptide analogs were studied by circular dichroism. Structure activity studies revealed that the substitution of specific amino acids and the incorporation of lipophilic groups enhanced the amphipathic α-helical conformation inducing better antimicrobial effects. Copyright © 2016 European Peptide Society and John Wiley & Sons, Ltd. Copyright © 2016 European Peptide Society and John Wiley & Sons, Ltd.

Thermophilic Bacillus coagulans requires less cellulases for simultaneous saccharification and fermentation of cellulose to products than mesophilic microbial biocatalysts.

PubMed

Ou, Mark S; Mohammed, Nazimuddin; Ingram, L O; Shanmugam, K T

2009-05-01

Ethanol production from lignocellulosic biomass depends on simultaneous saccharification of cellulose to glucose by fungal cellulases and fermentation of glucose to ethanol by microbial biocatalysts (SSF). The cost of cellulase enzymes represents a significant challenge for the commercial conversion of lignocellulosic biomass into renewable chemicals such as ethanol and monomers for plastics. The cellulase concentration for optimum SSF of crystalline cellulose with fungal enzymes and a moderate thermophile, Bacillus coagulans, was determined to be about 7.5 FPU g(-1) cellulose. This is about three times lower than the amount of cellulase required for SSF with Saccharomyces cerevisiae, Zymomonas mobilis, or Lactococcus lactis subsp. lactis whose growth and fermentation temperature optimum is significantly lower than that of the fungal cellulase activity. In addition, B. coagulans also converted about 80% of the theoretical yield of products from 40 g/L of crystalline cellulose in about 48 h of SSF with 10 FPU g(-1) cellulose while yeast, during the same period, only produced about 50% of the highest yield produced at end of 7 days of SSF. These results show that a match in the temperature optima for cellulase activity and fermentation is essential for decreasing the cost of cellulase in cellulosic ethanol production.

[Predominant strains of polycyclic aromatic hydrocarbon-degrading consortia from deep sea of the Middle Atlantic Ridge].

PubMed

Cui, Zhisong; Shao, Zongze

2009-07-01

In order to identify the predominant strains of polycyclic aromatic hydrocarbon (PAH)-degrading consortia harboring in sea water and surface sediment collected from deep sea of the Middle Atlantic Ridge. We employed enrichment method and spread-plate method to isolate cultivable bacteria and PAHs degraders from deep sea samples. Phylogenetic analysis was conducted by 16S rRNA gene sequencing of the bacteria. Then we analyzed the dominant bacteria in the PAHs-degrading consortia by denaturing gradient gel electrophoresis (DGGE) combined with DNA sequencing. Altogether 16 cultivable bacteria were obtained, including one PAHs degrader Novosphingobium sp. 4D. Phylogenetic analysis showed that strains closely related to Alcanivorax dieselolei NO1A (5/16) and Tistrella mobilis TISTR 1108T (5/16) constituted two biggest groups among the cultivable bacteria. DGGE analysis showed that strain 4L (also 4M and 4N, Alcanivorax dieselolei NO1A, 99.21%), 4D (Novosphingobium pentaromativorans US6-1(T), 97.07%) and 4B (also 4E, 4H and 4K, Tistrella mobilis TISTR 1108T, > 99%) dominated the consortium MC2D. While in consortium MC3CO, the predominant strains were strain 5C (also 5H, Alcanivorax dieselolei NO1A, > 99%), uncultivable strain represented by band 5-8 (Novosphingobium aromaticivorans DSM 12444T, 99.41%), 5J (Tistrella mobilis TISTR 1108T, 99.52%) and 5F (also 5G, Thalassospira lucentensis DSM 14000T, < 97%). We found that strains of genus Alcanivorax, Novosphingobium, Tistrella and Thalassospira were predominant bacteria of PAHs-degrading consortia in sea water and surface sediment of Middle Atlantic Ridge deep sea, with Novosphingobium spp. as their main PAHs degraders.

Comparison of endogenous loss and maintenance need for minerals in rainbow trout (Oncorhynchus mykiss) fed fishmeal or plant ingredient-based diets.

PubMed

Antony Jesu Prabhu, P; Kaushik, S J; Mariojouls, C; Surget, A; Fontagné-Dicharry, S; Schrama, J W; Geurden, I

2015-02-01

Mineral needs as affected by changes in dietary protein and oil sources were studied in rainbow trout. Duplicate groups (n = 30 fish per replicate) of rainbow trout (initial BW: 37 g) were fed either a fish meal/fish oil-based (M) or a complete plant ingredient (V)-based diet at four graded ration (R) levels [apparent satiation (AS), R75, R50 and R25 % of AS]; one treatment group was maintained under starvation. The feeding trial lasted 12 weeks at a water temperature of 17 °C. Dietary intake, apparent digestibility and initial and final whole-body composition data were used to calculate mineral gain which was regressed against digestible mineral intake (both expressed as mg or µg kg(-0.8) day(-1)). Starvation loss (SL), endogenous loss of fed fish (ELF, y-intercept at x = 0) and point of intake for zero balance (PZB, x-intercept at y = 0) were used as estimates of maintenance requirements. SL provided the lowest estimate, ELF provided the net requirement of a mineral for maintenance and PZB provided the digestible dietary intake required to meet maintenance (SL < ELF < PZB). Dietary ingredient composition did not significantly affect the digestible mineral supply required for maintenance (PZB) for any of the minerals (P, Mg, K, Cu and Zn) studied. However, ELF of micro-minerals such as Cu and Zn were significantly affected. The ELF of Cu was significantly lower and that of Zn was significantly higher in V group compared with M-fed fish. Further studies on the effects of such changes in dietary formulations on micro-mineral metabolism are warranted.

Xylose utilization in recombinant zymomonas

DOEpatents

Caimi, Perry G; McCole, Laura; Tao, Luan; Tomb, Jean-Francois; Viitanen, Paul V

2014-03-25

Xylose-utilizing Zymomonas strains studied were found to accumulate ribulose when grown in xylose-containing media. Engineering these strains to increase ribose-5-phosphate isomerase activity led to reduced ribulose accumulation, improved growth, improved xylose utilization, and increased ethanol production.

Development and application of co-culture for ethanol production by co-fermentation of glucose and xylose: a systematic review.

PubMed

Chen, Yanli

2011-05-01

This article reviews current co-culture systems for fermenting mixtures of glucose and xylose to ethanol. Thirty-five co-culture systems that ferment either synthetic glucose and xylose mixture or various biomass hydrolysates are examined. Strain combinations, fermentation modes and conditions, and fermentation performance for these co-culture systems are compared and discussed. It is noted that the combination of Pichia stipitis with Saccharomyces cerevisiae or its respiratory-deficient mutant is most commonly used. One of the best results for fermentation of glucose and xylose mixture is achieved by using co-culture of immobilized Zymomonas mobilis and free cells of P. stipitis, giving volumetric ethanol production of 1.277 g/l/h and ethanol yield of 0.49-0.50 g/g. The review discloses that, as a strategy for efficient conversion of glucose and xylose, co-culture fermentation for ethanol production from lignocellulosic biomass can increase ethanol yield and production rate, shorten fermentation time, and reduce process costs, and it is a promising technology although immature.

Pyruvate decarboxylase and alcohol dehydrogenase overexpression in Escherichia coli resulted in high ethanol production and rewired metabolic enzyme networks.

PubMed

Yang, Mingfeng; Li, Xuefeng; Bu, Chunya; Wang, Hui; Shi, Guanglu; Yang, Xiushan; Hu, Yong; Wang, Xiaoqin

2014-11-01

Pyruvate decarboxylase and alcohol dehydrogenase are efficient enzymes for ethanol production in Zymomonas mobilis. These two enzymes were over-expressed in Escherichia coli, a promising candidate for industrial ethanol production, resulting in high ethanol production in the engineered E. coli. To investigate the intracellular changes to the enzyme overexpression for homoethanol production, 2-DE and LC-MS/MS were performed. More than 1,000 protein spots were reproducibly detected in the gel by image analysis. Compared to the wild-type, 99 protein spots showed significant changes in abundance in the recombinant E. coli, in which 46 were down-regulated and 53 were up-regulated. Most proteins related to tricarboxylic acid cycle, glycerol metabolism and other energy metabolism were up-regulated, whereas proteins involved in glycolysis and glyoxylate pathway were down-regulated, indicating the rewired metabolism in the engineered E. coli. As glycolysis is the main pathway for ethanol production, and it was inhibited significantly in engineered E. coli, further efforts should be directed at minimizing the repression of glycolysis to optimize metabolism network for higher yields of ethanol production.

Replacing process water and nitrogen sources with biogas slurry during cellulosic ethanol production.

PubMed

You, Yang; Wu, Bo; Yang, Yi-Wei; Wang, Yan-Wei; Liu, Song; Zhu, Qi-Li; Qin, Han; Tan, Fu-Rong; Ruan, Zhi-Yong; Ma, Ke-Dong; Dai, Li-Chun; Zhang, Min; Hu, Guo-Quan; He, Ming-Xiong

2017-01-01

Environmental issues, such as the fossil energy crisis, have resulted in increased public attention to use bioethanol as an alternative renewable energy. For ethanol production, water and nutrient consumption has become increasingly important factors being considered by the bioethanol industry as reducing the consumption of these resources would decrease the overall cost of ethanol production. Biogas slurry contains not only large amounts of wastewater, but also the nutrients required for microbial growth, e.g., nitrogen, ammonia, phosphate, and potassium. Therefore, biogas slurry is an attractive potential resource for bioethanol production that could serve as an alternative to process water and nitrogen sources. In this study, we propose a method that replaces the process water and nitrogen sources needed for cellulosic ethanol production by Zymomonas mobilis with biogas slurry. To test the efficacy of these methods, corn straw degradation following pretreatment with diluted NaOH and enzymatic hydrolysis in the absence of fresh water was evaluated. Then, ethanol fermentation using the ethanologenic bacterial strain Z. mobilis ZMT2 was conducted without supplementing with additional nitrogen sources. After pretreatment with 1.34% NaOH (w/v) diluted in 100% biogas slurry and continuous enzymatic hydrolysis for 144 h, 29.19 g/L glucose and 12.76 g/L xylose were generated from 30 g dry corn straw. The maximum ethanol concentration acquired was 13.75 g/L, which was a yield of 72.63% ethanol from the hydrolysate medium. Nearly 94.87% of the ammonia nitrogen was depleted and no nitrate nitrogen remained after ethanol fermentation. The use of biogas slurry as an alternative to process water and nitrogen sources may decrease the cost of cellulosic ethanol production by 10.0-20.0%. By combining pretreatment with NaOH diluted in biogas slurry, enzymatic hydrolysis, and ethanol fermentation, 56.3 kg of ethanol was produced by Z. mobilis ZMT-2 through fermentation of 1000 kg of dried corn straw. In this study, biogas slurry replaced process water and nitrogen sources during cellulosic ethanol production. The results suggest that biogas slurry is a potential alternative to water when pretreating corn straw and, thus, has important potential applications in cellulosic ethanol production from corn straw. This study not only provides a novel method for utilizing biogas slurry, but also demonstrates a means of reducing the overall cost of cellulosic ethanol.

An in vivo, label-free quick assay for xylose transport in Escherichia coli.

PubMed

Chen, Tingjian; Zhang, Jingqing; Liang, Ling; Yang, Rong; Lin, Zhanglin

2009-07-01

Efficient use of xylose is necessary for economic production of biochemicals and biofuels from lignocellulosic materials. Current studies on xylose uptake for various microorganisms have been hampered by the lack of a facile assay for xylose transport. In this work, a rapid in vivo, label-free method for measuring xylose transport in Escherichia coli was developed by taking advantage of the Bacillus pumilus xylosidase (XynB), which cleaved a commercially available xylose analog, p-nitrophenyl-beta-d-xylopyranoside (pNPX), to release a chromogenic group, p-nitrophenol (pNP). XynB was expressed alone or in conjunction with a Zymomonas mobilis glucose facilitator protein (Glf) capable of transporting xylose. This XynB-mediated transport assay was demonstrated in test tubes and 96-well plates with submicromolar concentrations of pNPX. Kinetic inhibition experiments validated that pNPX and xylose were competitive substrates for the transport process, and the addition of glucose (20 g/L) in the culture medium clearly diminished the transmembrane transport of pNPX and, thus, mimicked its inhibitory action on xylose uptake. This method should be useful for engineering of the xylose transport process in E. coli, and similar assay schemes can be extended to other microorganisms.

Zymomonas with improved ethanol production in medium containing concentrated sugars and acetate

DOEpatents

Caimi, Perry G.; Chou, Yat-Chen; Franden, Mary Ann; Knoke, Kyle; Tao, Luan; Viitanen, Paul V.; Zhang, Min; Zhang, Yuying

2010-09-28

Through screening of a Zymomonas mutant library the himA gene was found to be involved in the inhibitory effect of acetate on Zymomonas performance. Xylose-utilizing Zymomonas further engineered to reduce activity of the himA gene were found to have increased ethanol production in comparison to a parental strain, when cultured in medium comprising xylose and acetate.

Impact of recycling stillage on conversion of dilute sulfuric acid pretreated corn stover to ethanol.

PubMed

Mohagheghi, Ali; Schell, Daniel J

2010-04-01

Both the current corn starch to ethanol industry and the emerging lignocellulosic biofuels industry view recycling of spent fermentation broth or stillage as a method to reduce fresh water use. The objective of this study was to understand the impact of recycling stillage on conversion of corn stover to ethanol. Sugars in a dilute-acid pretreated corn stover hydrolysate were fermented to ethanol by the glucose-xylose fermenting bacteria Zymomonas mobilis 8b. Three serial fermentations were performed at two different initial sugar concentrations using either 10% or 25% of the stillage as makeup water for the next fermentation in the series. Serial fermentations were performed to achieve near steady state concentration of inhibitors and other compounds in the corn stover hydrolysate. Little impact on ethanol yields was seen at sugar concentrations equivalent to pretreated corn stover slurry at 15% (w/w) with 10% recycle of the stillage. However, ethanol yields became progressively poorer as the sugar concentration increased and fraction of the stillage recycled increased. At an equivalent corn stover slurry concentration of 20% with 25% recycled stillage the ethanol yield was only 5%. For this microorganism with dilute-acid pretreated corn stover, recycling a large fraction of the stillage had a significant negative impact on fermentation performance. Although this finding is of concern for biochemical-based lignocellulose conversion processes, other microorganism/pretreatment technology combinations will likely perform differently. (c) 2009 Wiley Periodicals, Inc.

Pnp gene modification for improved xylose utilization in Zymomonas

DOEpatents

Caimi, Perry G G; Qi, Min; Tao, Luan; Viitanen, Paul V; Yang, Jianjun

2014-12-16

The endogenous pnp gene encoding polynucleotide phosphorylase in the Zymomonas genome was identified as a target for modification to provide improved xylose utilizing cells for ethanol production. The cells are in addition genetically modified to have increased expression of ribose-5-phosphate isomerase (RPI) activity, as compared to cells without this genetic modification, and are not limited in xylose isomerase activity in the absence of the pnp modification.

Zymomonas with improved ethanol production in medium containing concentrated sugars and acetate

DOEpatents

Caimi, Perry G [Kennett Square, PA; Chou, Yat-Chen [Lakewood, CO; Franden, Mary Ann [Centennial, CO; Knoke, Kyle [Newark, DE; Tao, Luan [Havertown, PA; Viitanen, Paul V [West Chester, PA; Zhang, Min [Lakewood, CO; Zhang, Yuying [New Hope, PA

2011-03-01

Through screening of a Zymomonas mutant library the himA gene was found to be involved in the inhibitory effect of acetate on Zymomonas performance. Xylose-utilizing Zymomonas strains further engineered to reduce activity of the himA gene were found to have increased ethanol production in comparison to a parental strain, when cultured in mixed-sugars medium comprising xylose, and, in particular, in the presence of acetate.

Zymomonas with improved xylose utilization in stress conditions

DOEpatents

Caimi, Perry G; Emptage, Mark; Li, Xu; Viitanen, Paul V; Chou, Yat-Chen; Franden, Mary Ann; Zhang, Min

2013-06-18

Strains of xylose utilizing Zymomonas with improved xylose utilization and ethanol production during fermentation in stress conditions were obtained using an adaptation method. The adaptation involved continuously growing xylose utilizing Zymomonas in media containing high sugars, acetic acid, ammonia, and ethanol.

Bidirectional reaction steps in metabolic networks: I. Modeling and simulation of carbon isotope labeling experiments.

PubMed

Wiechert, W; de Graaf, A A

1997-07-05

The extension of metabolite balancing with carbon labeling experiments, as described by Marx et al. (Biotechnol. Bioeng. 49: 11-29), results in a much more detailed stationary metabolic flux analysis. As opposed to basic metabolite flux balancing alone, this method enables both flux directions of bidirectional reaction steps to be quantitated. However, the mathematical treatment of carbon labeling systems is much more complicated, because it requires the solution of numerous balance equations that are bilinear with respect to fluxes and fractional labeling. In this study, a universal modeling framework is presented for describing the metabolite and carbon atom flux in a metabolic network. Bidirectional reaction steps are extensively treated and their impact on the system's labeling state is investigated. Various kinds of modeling assumptions, as usually made for metabolic fluxes, are expressed by linear constraint equations. A numerical algorithm for the solution of the resulting linear constrained set of nonlinear equations is developed. The numerical stability problems caused by large bidirectional fluxes are solved by a specially developed transformation method. Finally, the simulation of carbon labeling experiments is facilitated by a flexible software tool for network synthesis. An illustrative simulation study on flux identifiability from available flux and labeling measurements in the cyclic pentose phosphate pathway of a recombinant strain of Zymomonas mobilis concludes this contribution.

Pulque production from fermented agave sap as a dietary supplement in Prehispanic Mesoamerica.

PubMed

Correa-Ascencio, Marisol; Robertson, Ian G; Cabrera-Cortés, Oralia; Cabrera-Castro, Rubén; Evershed, Richard P

2014-09-30

Although in modern societies fermented beverages are associated with socializing, celebration, and ritual, in ancient times they were also importa`nt sources of essential nutrients and potable water. In Mesoamerica, pulque, an alcoholic beverage produced from the fermented sap of several species of maguey plants (Agavaceae; Fig. 1) is hypothesized to have been used as a dietary supplement and risk-buffering food in ancient Teotihuacan (150 B.C. to A.D. 650). Although direct archaeological evidence of pulque production is lacking, organic residue analysis of pottery vessels offers a new avenue of investigation. However, the chemical components of alcoholic beverages are water-soluble, greatly limiting their survival over archaeological timescales compared with hydrophobic lipids widely preserved in food residues. Hence, we apply a novel lipid biomarker approach that considers detection of bacteriohopanoids derived from the ethanol-producing bacterium Zymomonas mobilis for identifying pulque production/consumption in pottery vessels. Gas chromatography-mass spectrometry selected ion monitoring (m/z 191) of lipid extracts of >300 potsherds revealed characteristic bacteriohopanoid distributions in a subset of 14 potsherds. This hopanoid biomarker approach offers a new means of identifying commonly occurring bacterially fermented alcoholic beverages worldwide, including palm wine, beer, cider, perry, and other plant sap- or fruit-derived beverages [Swings J, De Ley J (1977) Bacteriol Rev 41(1):1-46].

A comparison of simple rheological parameters and simulation data for Zymomonas mobilis fermentation broths with high substrate loading in a 3-L bioreactor.

PubMed

Um, Byung-Hwan; Hanley, Thomas R

2008-03-01

Traditionally, as much as 80% or more of an ethanol fermentation broth is water that must be removed. This mixture is not only costly to separate but also produces a large aqueous stream that must then be disposed of or recycled. Integrative approaches to water reduction include increasing the biomass concentration during fermentation. In this paper, experimental results are presented for the rheological behavior of high-solids enzymatic cellulose hydrolysis and ethanol fermentation for biomass conversion using Solka Floc as the model feedstock. The experimental determination of the viscosity, shear stress, and shear rate relationships of the 10 to 20% slurry concentrations with constant enzyme concentrations are performed with a variable speed rotational viscometer (2.0 to 200 rpm) at 40 degrees C. The viscosities of enzymatic suspension observed were in range of 0.0418 to 0.0144, 0.233 to 0.0348, and 0.292 to 0.0447 Pa s for shear rates up to 100 reciprocal seconds at 10, 15, and 20% initial solids (w/v), respectively. Computational fluid dynamics analysis of bioreactor mixing demonstrates the change in bioreactor mixing with increasing biomass concentration. The portion-loading method is shown to be effective for processing high-solids slurries.

A Comparison of Simple Rheological Parameters and Simulation Data for Zymomonas mobilis Fermentation Broths with High Substrate Loading in a 3-L Bioreactor

NASA Astrophysics Data System (ADS)

Um, Byung-Hwan; Hanley, Thomas R.

Traditionally, as much as 80% or more of an ethanol fermentation broth is water that must be removed. This mixture is not only costly to separate but also produces a large aqueous stream that must then be disposed of or recycled. Integrative approaches to water reduction include increasing the biomass concentration during fermentation. In this paper, experimental results are presented for the rheological behavior of high-solids enzymatic cellulose hydrolysis and ethanol fermentation for biomass conversion using Solka Floc as the model feedstock. The experimental determination of the viscosity, shear stress, and shear rate relationships of the 10 to 20% slurry concentrations with constant enzyme concentrations are performed with a variable speed rotational viscometer (2.0 to 200 rpm) at 40 °C. The viscosities of enzymatic suspension observed were in range of 0.0418 to 0.0144, 0.233 to 0.0348, and 0.292 to 0.0447 Pa s for shear rates up to 100 reciprocal seconds at 10, 15, and 20% initial solids (w/v), respectively. Computational fluid dynamics analysis of bioreactor mixing demonstrates the change in bioreactor mixing with increasing biomass concentration. The portion-loading method is shown to be effective for processing highsolids slurries.

Pantothenic acid biosynthesis in zymomonas

DOEpatents

Tao, Luan; Tomb, Jean-Francois; Viitanen, Paul V.

2014-07-01

Zymomonas is unable to synthesize pantothenic acid and requires this essential vitamin in growth medium. Zymomonas strains transformed with an operon for expression of 2-dehydropantoate reductase and aspartate 1-decarboxylase were able to grow in medium lacking pantothenic acid. These strains may be used for ethanol production without pantothenic acid supplementation in seed culture and fermentation media.

Permanent draft genome sequence of Desulfurococcus mobilis type strain DSM 2161, a thermoacidophilic sulfur-reducing crenarchaeon isolated from acidic hot springs of Hveravellir, Iceland.

PubMed

Susanti, Dwi; Johnson, Eric F; Lapidus, Alla; Han, James; Reddy, T B K; Pilay, Manoj; Ivanova, Natalia N; Markowitz, Victor M; Woyke, Tanja; Kyrpides, Nikos C; Mukhopadhyay, Biswarup

2016-01-01

This report presents the permanent draft genome sequence of Desulfurococcus mobilis type strain DSM 2161, an obligate anaerobic hyperthermophilic crenarchaeon that was isolated from acidic hot springs in Hveravellir, Iceland. D. mobilis utilizes peptides as carbon and energy sources and reduces elemental sulfur to H2S. A metabolic construction derived from the draft genome identified putative pathways for peptide degradation and sulfur respiration in this archaeon. Existence of several hydrogenase genes in the genome supported previous findings that H2 is produced during the growth of D. mobilis in the absence of sulfur. Interestingly, genes encoding glucose transport and utilization systems also exist in the D. mobilis genome though this archaeon does not utilize carbohydrate for growth. The draft genome of D. mobilis provides an additional mean for comparative genomic analysis of desulfurococci. In addition, our analysis on the Average Nucleotide Identity between D. mobilis and Desulfurococcus mucosus suggested that these two desulfurococci are two different strains of the same species.

Permanent draft genome sequence of Desulfurococcus mobilis type strain DSM 2161, a thermoacidophilic sulfur-reducing crenarchaeon isolated from acidic hot springs of Hveravellir, Iceland

DOE Office of Scientific and Technical Information (OSTI.GOV)

Susanti, Dwi; Johnson, Eric F.; Lapidus, Alla

Our report presents the permanent draft genome sequence of Desulfurococcus mobilis type strain DSM 2161, an obligate anaerobic hyperthermophilic crenarchaeon that was isolated from acidic hot springs in Hveravellir, Iceland. D. mobilis utilizes peptides as carbon and energy sources and reduces elemental sulfur to H 2S. A metabolic construction derived from the draft genome identified putative pathways for peptide degradation and sulfur respiration in this archaeon. Existence of several hydrogenase genes in the genome supported previous findings that H 2 is produced during the growth of D. mobilis in the absence of sulfur. Interestingly, genes encoding glucose transport and utilizationmore » systems also exist in the D. mobilis genome though this archaeon does not utilize carbohydrate for growth. The draft genome of D. mobilis provides an additional mean for comparative genomic analysis of desulfurococci. In addition, our analysis on the Average Nucleotide Identity between D. mobilis and Desulfurococcus mucosus suggested that these two desulfurococci are two different strains of the same species.« less

Permanent draft genome sequence of Desulfurococcus mobilis type strain DSM 2161, a thermoacidophilic sulfur-reducing crenarchaeon isolated from acidic hot springs of Hveravellir, Iceland

DOE PAGES

Susanti, Dwi; Johnson, Eric F.; Lapidus, Alla; ...

2016-01-13

Our report presents the permanent draft genome sequence of Desulfurococcus mobilis type strain DSM 2161, an obligate anaerobic hyperthermophilic crenarchaeon that was isolated from acidic hot springs in Hveravellir, Iceland. D. mobilis utilizes peptides as carbon and energy sources and reduces elemental sulfur to H 2S. A metabolic construction derived from the draft genome identified putative pathways for peptide degradation and sulfur respiration in this archaeon. Existence of several hydrogenase genes in the genome supported previous findings that H 2 is produced during the growth of D. mobilis in the absence of sulfur. Interestingly, genes encoding glucose transport and utilizationmore » systems also exist in the D. mobilis genome though this archaeon does not utilize carbohydrate for growth. The draft genome of D. mobilis provides an additional mean for comparative genomic analysis of desulfurococci. In addition, our analysis on the Average Nucleotide Identity between D. mobilis and Desulfurococcus mucosus suggested that these two desulfurococci are two different strains of the same species.« less

Enabling Unbalanced Fermentations by Using Engineered Electrode-Interfaced Bacteria

PubMed Central

Flynn, Jeffrey M.; Ross, Daniel E.; Hunt, Kristopher A.; Bond, Daniel R.; Gralnick, Jeffrey A.

2010-01-01

Cellular metabolism is a series of tightly linked oxidations and reductions that must be balanced. Recycling of intracellular electron carriers during fermentation often requires substrate conversion to undesired products, while respiration demands constant addition of electron acceptors. The use of electrode-based electron acceptors to balance biotransformations may overcome these constraints. To test this hypothesis, the metal-reducing bacterium Shewanella oneidensis was engineered to stoichiometrically convert glycerol into ethanol, a biotransformation that will not occur unless two electrons are removed via an external reaction, such as electrode reduction. Multiple modules were combined into a single plasmid to alter S. oneidensis metabolism: a glycerol module, consisting of glpF, glpK, glpD, and tpiA from Escherichia coli, and an ethanol module containing pdc and adh from Zymomonas mobilis. A further increase in product yields was accomplished through knockout of pta, encoding phosphate acetyltransferase, shifting flux toward ethanol and away from acetate production. In this first-generation demonstration, conversion of glycerol to ethanol required the presence of an electrode to balance the reaction, and electrode-linked rates were on par with volumetric conversion rates observed in engineered E. coli. Linking microbial biocatalysis to current production can eliminate redox constraints by shifting other unbalanced reactions to yield pure products and serve as a new platform for next-generation bioproduction strategies. PMID:21060736

Pulque production from fermented agave sap as a dietary supplement in Prehispanic Mesoamerica

PubMed Central

Correa-Ascencio, Marisol; Robertson, Ian G.; Cabrera-Cortés, Oralia; Cabrera-Castro, Rubén; Evershed, Richard P.

2014-01-01

Although in modern societies fermented beverages are associated with socializing, celebration, and ritual, in ancient times they were also importa`nt sources of essential nutrients and potable water. In Mesoamerica, pulque, an alcoholic beverage produced from the fermented sap of several species of maguey plants (Agavaceae; Fig. 1) is hypothesized to have been used as a dietary supplement and risk-buffering food in ancient Teotihuacan (150 B.C. to A.D. 650). Although direct archaeological evidence of pulque production is lacking, organic residue analysis of pottery vessels offers a new avenue of investigation. However, the chemical components of alcoholic beverages are water-soluble, greatly limiting their survival over archaeological timescales compared with hydrophobic lipids widely preserved in food residues. Hence, we apply a novel lipid biomarker approach that considers detection of bacteriohopanoids derived from the ethanol-producing bacterium Zymomonas mobilis for identifying pulque production/consumption in pottery vessels. Gas chromatography–mass spectrometry selected ion monitoring (m/z 191) of lipid extracts of >300 potsherds revealed characteristic bacteriohopanoid distributions in a subset of 14 potsherds. This hopanoid biomarker approach offers a new means of identifying commonly occurring bacterially fermented alcoholic beverages worldwide, including palm wine, beer, cider, perry, and other plant sap- or fruit-derived beverages [Swings J, De Ley J (1977) Bacteriol Rev 41(1):1–46]. PMID:25225408

Arsenic-Rich Polyarsenides Stabilized by Cp*Fe Fragments.

PubMed

Schmidt, Monika; Konieczny, David; Peresypkina, Eugenia V; Virovets, Alexander V; Balázs, Gabor; Bodensteiner, Michael; Riedlberger, Felix; Krauss, Hannes; Scheer, Manfred

2017-06-12

The redox chemistry of [Cp*Fe(η 5 -As 5 )] (1, Cp*=η 5 -C 5 Me 5 ) has been investigated by cyclic voltammetry, revealing a redox behavior similar to that of its lighter congener [Cp*Fe(η 5 -P 5 )]. However, the subsequent chemical reduction of 1 by KH led to the formation of a mixture of novel As n scaffolds with n up to 18 that are stabilized only by [Cp*Fe] fragments. These include the arsenic-poor triple-decker complex [K(dme) 2 ][{Cp*Fe(μ,η 2:2 -As 2 )} 2 ] (2) and the arsenic-rich complexes [K(dme) 3 ] 2 [(Cp*Fe) 2 (μ,η 4:4 -As 10 )] (3), [K(dme) 2 ] 2 [(Cp*Fe) 2 (μ,η 2:2:2:2 -As 14 )] (4), and [K(dme) 3 ] 2 [(Cp*Fe) 4 (μ 4 ,η 4:3:3:2:2:1:1 -As 18 )] (5). Compound 4 and the polyarsenide complex 5 are the largest anionic As n ligand complexes reported thus far. Complexes 2-5 were characterized by single-crystal X-ray diffraction, 1 H NMR spectroscopy, EPR spectroscopy (2), and mass spectrometry. Furthermore, DFT calculations showed that the intermediate [Cp*Fe(η 5 -As 5 )] - , which is presumably formed first, undergoes fast dimerization to the dianion [(Cp*Fe) 2 (μ,η 4:4 -As 10 )] 2- . © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Monitoring microbial growth and activity using spectral induced polarization and low-field nuclear magnetic resonance

NASA Astrophysics Data System (ADS)

Zhang, Chi; Keating, Kristina; Revil, Andre

2015-04-01

Microbes and microbial activities in the Earth's subsurface play a significant role in shaping subsurface environments and are involved in environmental applications such as remediation of contaminants in groundwater and oil fields biodegradation. Stimulated microbial growth in such applications could cause wide variety of changes of physical/chemical properties in the subsurface. It is critical to monitor and determine the fate and transportation of microorganisms in the subsurface during such applications. Recent geophysical studies demonstrate the potential of two innovative techniques, spectral induced polarization (SIP) and low-field nuclear magnetic resonance (NMR), for monitoring microbial growth and activities in porous media. The SIP measures complex dielectric properties of porous media at low frequencies of exciting electric field, and NMR studies the porous structure of geologic media and characterizes fluids subsurface. In this laboratory study, we examined both SIP and NMR responses from bacterial growth suspension as well as suspension mixed with silica sands. We focus on the direct contribution of microbes to the SIP and NMR signals in the absence of biofilm formation or biomineralization. We used Zymomonas mobilis and Shewanella oneidensis (MR-1) for SIP and NMR measurements, respectively. The SIP measurements were collected over the frequency range of 0.1 - 1 kHz on Z. mobilis growth suspension and suspension saturated sands at different cell densities. SIP data show two distinct peaks in imaginary conductivity spectra, and both imaginary and real conductivities increased as microbial density increased. NMR data were collected using both CPMG pulse sequence and D-T2 mapping to determine the T2-distribution and diffusion properties on S. oneidensis suspension, pellets (live and dead), and suspension mixed with silica sands. NMR data show a decrease in the T2-distribution in S. oneidensis suspension saturated sands as microbial density increase. A clear distinction in the T2-distribution and D-T2 plots between live and dead cell pellets was also observed. These results will provide a basis for understanding the effect of microbes within geologic media on SIP and low-field NMR measurements. This research suggests that both SIP and NMR have the potential to monitor microbial growth and activities in the subsurface and could provide spatiotemporal variations in bacterial abundance in porous media.

Fine structure and ecdysis of mandibular sensilla associated with the lacinia mobilis in Neomysis integer (Leach, 1814) (Crustacea, Malacostraca, Peracarida).

PubMed

Geiselbrecht, Hannes; Melzer, Roland R

2014-05-01

The external and internal structures of adult Neomysis integer mandibles were studied using light and electron microscopy with special reference to the lacinia mobilis, a highly specialized appendage on the gnathal edge of many crustaceans. The right and left lacinia mobilis are equipped with ciliary primary sensory cells revealing that both laciniae are also mechanosensory organs in addition to their mechanical function during mastication. A detailed character analyses indicated that the right lacinia is probably a highly derived sensory seta, whereas two alternative interpretations are considered for the left lacinia; it could be a sensillar appendage equipped with two mechanosensory units, or it could be a movable appendage of the incisor process containing two sensilla deprived of external appendages. The ecdysis of the lacinia mobilis corresponds very well to type I sensillar ecdysis, suggesting classification as a sensillar appendage. These features support a possible homology of the right lacinia mobilis in Peracarida and Decapoda, tracing them to an origin as a member of the setal row. Whether the left lacinia mobilis is a sensillum or an appendage with sensilla cannot be resolved presently. Copyright © 2014 Elsevier Ltd. All rights reserved.

Novel Xylose Dehydrogenase in the Halophilic Archaeon Haloarcula marismortui†

PubMed Central

Johnsen, Ulrike; Schönheit, Peter

2004-01-01

During growth of the halophilic archaeon Haloarcula marismortui on d-xylose, a specific d-xylose dehydrogenase was induced. The enzyme was purified to homogeneity. It constitutes a homotetramer of about 175 kDa and catalyzed the oxidation of xylose with both NADP+ and NAD+ as cosubstrates with 10-fold higher affinity for NADP+. In addition to d-xylose, d-ribose was oxidized at similar kinetic constants, whereas d-glucose was used with about 70-fold lower catalytic efficiency (kcat/Km). With the N-terminal amino acid sequence of the subunit, an open reading frame (ORF)—coding for a 39.9-kDA protein—was identified in the partially sequenced genome of H. marismortui. The function of the ORF as the gene designated xdh and coding for xylose dehydrogenase was proven by its functional overexpression in Escherichia coli. The recombinant enzyme was reactivated from inclusion bodies following solubilization in urea and refolding in the presence of salts, reduced and oxidized glutathione, and substrates. Xylose dehydrogenase showed the highest sequence similarity to glucose-fructose oxidoreductase from Zymomonas mobilis and other putative bacterial and archaeal oxidoreductases. Activities of xylose isomerase and xylulose kinase, the initial reactions of xylose catabolism of most bacteria, could not be detected in xylose-grown cells of H. marismortui, and the genes that encode them, xylA and xylB, were not found in the genome of H. marismortui. Thus, we propose that this first characterized archaeal xylose dehydrogenase catalyzes the initial step in xylose degradation by H. marismortui. PMID:15342590

Enhanced production of nargenicin A1 and creation of a novel derivative using a synthetic biology platform.

PubMed

Dhakal, Dipesh; Chaudhary, Amit Kumar; Yi, Jeong Sang; Pokhrel, Anaya Raj; Shrestha, Biplav; Parajuli, Prakash; Shrestha, Anil; Yamaguchi, Tokutaro; Jung, Hye Jin; Kim, Seung-Young; Kim, Byung-Gee; Sohng, Jae Kyung

2016-12-01

Nargenicin A1, an antibacterial produced by Nocardia sp. CS682 (KCTC 11297BP), demonstrates effective activity against various Gram-positive bacteria. Hence, we attempted to enhance nargenicin A1 production by utilizing the cumulative effect of synthetic biology, metabolic engineering and statistical media optimization strategies. To facilitate the modular assembly of multiple genes for genetic engineering in Nocardia sp. CS682, we constructed a set of multi-monocistronic vectors, pNV18L1 and pNV18L2 containing hybrid promoter (derived from ermE* and promoter region of neo r ), ribosome binding sites (RBS), and restriction sites for cloning, so that each cloned gene was under its own promoter and RBS. The multi-monocistronic vector, pNV18L2 containing transcriptional terminator showed better efficiency in reporter gene assay. Thus, multiple genes involved in the biogenesis of pyrrole moiety (ngnN2, ngnN3, ngnN4, and ngnN5 from Nocardia sp. CS682), glucose utilization (glf and glk from Zymomonas mobilis), and malonyl-CoA synthesis (accA2 and accBE from Streptomyces coelicolor A3 (2)), were cloned in pNV18L2. Further statistical optimization of specific precursors (proline and glucose) and their feeding time led to ~84.9 mg/L nargenicin from Nocardia sp. GAP, which is ~24-fold higher than Nocardia sp. CS682 (without feeding). Furthermore, pikC from Streptomyces venezuelae was expressed to generate Nocardia sp. PikC. Nargenicin A1 acid was characterized as novel derivative of nargenicin A1 produced from Nocardia sp. PikC by mass spectrometry (MS) and nuclear magnetic resonance (NMR) analyses. We also performed comparative analysis of the anticancer and antibacterial activities of nargenicin A1 and nargenicin A1 acid, which showed a reduction in antibacterial potential for nargenicin A1 acid. Thus, the development of an efficient synthetic biological platform provided new avenues for enhancing or structurally diversifying nargenicin A1 by means of pathway designing and engineering.

Fuel alcohol biosynthesis by Zymomonas anaerobia: optimization studies

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kosaric, N.; Ong, S.L.; Davnjak, Z.

1982-03-01

The optimum operating conditions for growth and ethanol production of Zymomonas anaerobia ATCC 29501 were established. The optimum pH range and temperature were found to be 5.0-6.0 and 35/sup 0/C, respectively. Based on the results obtained from the temperature optimization study, an Arrhenius-type temperature relationship for the specific growth rate was developed. The growth and ethanol production of this microbe also have been optimized in terms of concentrations of glucose, essential nutrients, and minerals. With optimum medium and operating conditions, an ethanol concentration of 96 g/L was obtained in 23h. Both growth and ethanol yield coefficients in dependence on initialmore » glucose concentrations were determined.« less

Fuel alcohol biosynthesis by Zymomonas anaerobia: optimization studies

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kosaric, N.; Ong, S.L.; Duvnjak, Z.

1982-03-01

The optimum operating conditions for growth and ethanol production of Zymomonas anaerobia ATCC 29501 were established. The optimum pH range and temperature were found to be 5.0-6.0 and 35 degrees C, respectively. Based on the results obtained from the temperature optimization study, an Arrhenius-type temperature relationship for the specific growth rate was developed. The growth and ethanol production of this microbe also have been optimized in terms of concentrations of glucose, essential nutrients, and minerals. With optimum medium and operating conditions, an ethanol concentration of 96 g/L was obtained in 23 hours. Both growth and ethanol yield coefficients in dependencemore » on initial glucose concentrations were determined. (Refs. 16).« less

Comparative fermentation behaviour and chemical characteristics of Saccharomyces and Zymomonas fermented culled apple juice.

PubMed

Sandhu, D K; Joshi, V K

1994-12-01

Ethanol production from culled apple juice showed that fermentability of the juice could be enhanced by addition of DAHP or ammonium sulphate in Saccharomyces and DAHP in Zymomonas fermentation. Addition of trace elements inhibited both the fermentations and ethanol, consequently. With respect to by-products of fermentation, no clear advantage of Zymomnas fermentation of culled apple juice could be observed. Differences in physico-chemical characteristics of the fermented apple juice were also noted. Saccharomyces cerevisiae proved to be better than Zymomonas in most of the parameters and is preferrable from handling and spoilage point of view.

Enterobacter aerogenes Hormaeche and Edwards 1960 (Approved Lists 1980) and Klebsiella mobilis Bascomb et al. 1971 (Approved Lists 1980) share the same nomenclatural type (ATCC 13048) on the Approved Lists and are homotypic synonyms, with consequences for the name Klebsiella mobilis Bascomb et al. 1971 (Approved Lists 1980).

PubMed

Tindall, B J; Sutton, G; Garrity, G M

2017-02-01

Enterobacter aerogenes Hormaeche and Edwards 1960 (Approved Lists 1980) and Klebsiella mobilis Bascomb et al. 1971 (Approved Lists 1980) were placed on the Approved Lists of Bacterial Names and were based on the same nomenclatural type, ATCC 13048. Consequently they are to be treated as homotypic synonyms. However, the names of homotypic synonyms at the rank of species normally are based on the same epithet. Examination of the Rules of the International Code of Nomenclature of Bacteria in force at the time indicates that the epithet mobilis in Klebsiella mobilis Bascomb et al. 1971 (Approved Lists 1980) was illegitimate at the time the Approved Lists were published and according to the Rules of the current International Code of Nomenclature of Prokaryotes continues to be illegitimate.

2,5-dimethylthiophene coordination to three metal centers in (. eta. sup 4 ,S-. mu. sub 3 -2,5-Me sub 2 T)(IrCp sup * )(Mo(CO) sub 2 Cp) sub 2

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chen, Jiabi; Angelici, R.J.

1990-03-01

The reaction of Cp{sup *}Ir({eta}{sup 4}-2,5-Me{sub 2}T), where {eta}{sup 4}-2,5-Me{sub 2}T is 2,5-dimethylthiophene coordinated through the four ring carbons, with Cp(CO){sub 2}Mo{triple bond}Mo(CO){sub 2}Cp gives ({eta}{sup 4},S-{mu}{sub 3}-2,5-Me{sub 2}T)(IrCp{sup *})(Mo(CO){sub 2}Cp){sub 2}, in which the bridging thiophene is {eta}{sup 4}-coordinated to the Ir and bonded via the sulfur to both Mo atoms. The same product is obtained from the ring-opened isomer of Cp{sup *}Ir(2,5-Me{sub 2}T). The structure of the product, which is the first example of a thiophene coordinated to three metal centers, was established by X-ray crystallography.

Ethanol production using xylitol synthesis mutant of xylose-utilizing zymomonas

DOEpatents

Viitanen, Paul V.; McCutchen, Carol M.; Emptage, Mark; Caimi, Perry G.; Zhang, Min; Chou, Yat-Chen

2010-06-22

Production of ethanol using a strain of xylose-utilizing Zymomonas with a genetic modification of the glucose-fructose oxidoreductase gene was found to be improved due to greatly reduced production of xylitol, a detrimental by-product of xylose metabolism synthesized during fermentation.

Reactivity of cyclopentadienyl transition metal(ii) complexes with borate ligands: structural characterization of the toluene-activated molybdenum complex [Cp*Mo(CO)2(η3-CH2C6H5)].

PubMed

Ramalakshmi, Rongala; Maheswari, K; Sharmila, Dudekula; Paul, Anamika; Roisnel, Thierry; Halet, Jean-François; Ghosh, Sundargopal

2016-10-18

Reactions of cyclopentadienyl transition-metal halide complexes [Cp*Mo(CO) 3 Cl], 1, and [CpFe(CO) 2 I], 2, (Cp = C 5 H 5 ; Cp* = η 5 -C 5 Me 5 ) with borate ligands are reported. Treatment of 1 with [NaBt 2 ] (Bt 2 = dihydrobis(2-mercapto-benzothiazolyl)borate) in toluene yielded [Cp*Mo(CO) 2 (C 7 H 4 S 2 N)], 3, and [Cp*Mo(CO) 2 (η 3 -CH 2 C 6 H 5 )], 4, with a selective binding of toluene through C-H activation followed by orthometallation. Note that compound 4 is a structurally characterized toluene-activated molecule in which the metal is in η 3 -coordination mode. Under similar reaction conditions, [NaPy 2 ] (Py 2 = dihydrobis(2-mercaptopyridyl)borate) produced only the mercaptopyridyl molybdenum complex [Cp*Mo(CO) 2 (C 5 H 4 SN)], 5, in good yield. On the other hand, when compound 2 was treated individually with [NaBt] (Bt = trihydro(2-mercapto-benzothiazolyl)borate) and [NaPy 2 ] in THF, formation of the η 1 -coordinated complexes [CpFe(CO) 2 (C 7 H 4 S 2 N)], 6, and [CpFe(CO) 2 (C 5 H 4 SN)], 7, was observed. The solid-state molecular structures of compounds 3, 4, 6, and 7 have been established by single-crystal X-ray crystallographic analyses.

Some transition metal complexes derived from mono- and di-ethynyl perfluorobenzenes.

PubMed

Armitt, David J; Bruce, Michael I; Gaudio, Maryka; Zaitseva, Natasha N; Skelton, Brian W; White, Allan H; Le Guennic, Boris; Halet, Jean-François; Fox, Mark A; Roberts, Rachel L; Hartl, Frantisek; Low, Paul J

2008-12-21

Transition metal alkynyl complexes containing perfluoroaryl groups have been prepared directly from trimethylsilyl-protected mono- and di-ethynyl perfluoroarenes by simple desilylation/metallation reaction sequences. Reactions between Me(3)SiC[triple bond, length as m-dash]CC(6)F(5) and RuCl(dppe)Cp' [Cp' = Cp, Cp*] in the presence of KF in MeOH give the monoruthenium complexes Ru(C[triple bond, length as m-dash]CC(6)F(5))(dppe)Cp' [Cp' = Cp (); Cp* ()], which are related to the known compound Ru(C[triple bond, length as m-dash]CC(6)F(5))(PPh(3))(2)Cp (). Treatment of Me(3)SiC[triple bond, length as m-dash]CC(6)F(5) with Pt(2)(mu-dppm)(2)Cl(2) in the presence of NaOMe in MeOH gave the bis(alkynyl) complex Pt(2)(mu-dppm)(2)(C[triple bond, length as m-dash]CC(6)F(5))(2) (). The Pd(0)/Cu(i)-catalysed reactions between Au(C[triple bond, length as m-dash]CC(6)F(5))(PPh(3)) and Mo( identical withCBr)(CO)(2)Tp* [Tp* = hydridotris(3.5-dimethylpyrazoyl)borate], Co(3)(mu(3)-CBr)(mu-dppm)(CO)(7) or IC[triple bond, length as m-dash]CFc [Fc = (eta(5)-C(5)H(4))FeCp] afford Mo( identical withCC[triple bond, length as m-dash]CC(6)F(5))(CO)(2)Tp* (), Co(3)(mu(3)-CC[triple bond, length as m-dash]CC(6)F(5))(mu-dppm)(CO)(7) () and FcC[triple bond, length as m-dash]CC[triple bond, length as m-dash]CC(6)F(5) (), respectively. The diruthenium complexes 1,4-{Cp'(PP)RuC[triple bond, length as m-dash]C}(2)C(6)F(4) [(PP)Cp' = (PPh(3))(2)Cp (); (dppe)Cp (); (dppe)Cp* ()] are prepared from 1,4-(Me(3)SiC[triple bond, length as m-dash]C)(2)C(6)F(4) in a manner similar to that described for the monoruthenium complexes -. The non-fluorinated complexes 1,4-{Cp'(PP)RuC[triple bond, length as m-dash]C}(2)C(6)H(4) [(PP)Cp' = (PPh(3))(2)Cp (); (dppe)Cp (); (dppe)Cp* ()], prepared for comparison, are obtained from 1,4-(Me(3)SiC[triple bond, length as m-dash]C)(2)C(6)H(4). Spectro-electrochemical studies of the ruthenium aryl and arylene alkynyl complexes - and -, together with DFT-based computational studies on suitable model systems, indicate that perfluorination of the aromatic ring has little effect on the electronic structures of these compounds, and that the frontier orbitals have appreciable diethynylphenylene character. Molecular structure determinations are reported for the fluoroaromatic complexes , , , and .

Analysis of bacterial community during the fermentation of pulque, a traditional Mexican alcoholic beverage, using a polyphasic approach.

PubMed

Escalante, Adelfo; Giles-Gómez, Martha; Hernández, Georgina; Córdova-Aguilar, María Soledad; López-Munguía, Agustín; Gosset, Guillermo; Bolívar, Francisco

2008-05-31

In this study, the characterization of the bacterial community present during the fermentation of pulque, a traditional Mexican alcoholic beverage from maguey (Agave), was determined for the first time by a polyphasic approach in which both culture and non-culture dependent methods were utilized. The work included the isolation of lactic acid bacteria (LAB), aerobic mesophiles, and 16S rDNA clone libraries from total DNA extracted from the maguey sap (aguamiel) used as substrate, after inoculation with a sample of previously produced pulque and followed by 6-h fermentation. Microbiological diversity results were correlated with fermentation process parameters such as sucrose, glucose, fructose and fermentation product concentrations. In addition, medium rheological behavior analysis and scanning electron microscopy in aguamiel and during pulque fermentation were also performed. Our results showed that both culture and non-culture dependent approaches allowed the detection of several new and previously reported species within the alpha-, gamma-Proteobacteria and Firmicutes. Bacteria diversity in aguamiel was composed by the heterofermentative Leuconostoc citreum, L. mesenteroides, L. kimchi, the gamma-Proteobacteria Erwinia rhapontici, Enterobacter spp. and Acinetobacter radioresistens. Inoculation with previously fermented pulque incorporated to the system microbiota, homofermentative lactobacilli related to Lactobacillus acidophilus, several alpha-Proteobacteria such as Zymomonas mobilis and Acetobacter malorum, other gamma-Proteobacteria and an important amount of yeasts, creating a starting metabolic diversity composed by homofermentative and heterofermentative LAB, acetic and ethanol producing microorganisms. At the end of the fermentation process, the bacterial diversity was mainly composed by the homofermentative Lactobacillus acidophilus, the heterofermentative L. mesenteroides, Lactococcus lactis subsp. lactis and the alpha-Proteobacteria A. malorum. After a 6-h fermentation, 83.27% of total sugars detected after inoculation were consumed (228.4 mM hexose equivalents) and a carbon (C) recovery of 66.18% in fermentation products was estimated. They were produced 284.4 mM C as ethanol, 71.5 mM C as acetic acid and 19 mM C as lactic acid, demonstrating the presence of homo- and heterofermentative, acetic and alcoholic metabolisms in the final product. It was also found, after hydrolysis, that the exopolysaccharide produced during the fermentation was mainly composed by fructose residues, probably inulin or levan.

A novel aldose-aldose oxidoreductase for co-production of D-xylonate and xylitol from D-xylose with Saccharomyces cerevisiae.

PubMed

Wiebe, Marilyn G; Nygård, Yvonne; Oja, Merja; Andberg, Martina; Ruohonen, Laura; Koivula, Anu; Penttilä, Merja; Toivari, Mervi

2015-11-01

An open reading frame CC1225 from the Caulobacter crescentus CB15 genome sequence belongs to the Gfo/Idh/MocA protein family and has 47 % amino acid sequence identity with the glucose-fructose oxidoreductase from Zymomonas mobilis (Zm GFOR). We expressed the ORF CC1225 in the yeast Saccharomyces cerevisiae and used a yeast strain expressing the gene coding for Zm GFOR as a reference. Cell extracts of strains overexpressing CC1225 (renamed as Cc aaor) showed some Zm GFOR type of activity, producing D-gluconate and D-sorbitol when a mixture of D-glucose and D-fructose was used as substrate. However, the activity in Cc aaor expressing strain was >100-fold lower compared to strains expressing Zm gfor. Interestingly, C. crescentus AAOR was clearly more efficient than the Zm GFOR in converting in vitro a single sugar substrate D-xylose (10 mM) to xylitol without an added cofactor, whereas this type of activity was very low with Zm GFOR. Furthermore, when cultured in the presence of D-xylose, the S. cerevisiae strain expressing Cc aaor produced nearly equal concentrations of D-xylonate and xylitol (12.5 g D-xylonate l(-1) and 11.5 g D-xylitol l(-1) from 26 g D-xylose l(-1)), whereas the control strain and strain expressing Zm gfor produced only D-xylitol (5 g l(-1)). Deletion of the gene encoding the major aldose reductase, Gre3p, did not affect xylitol production in the strain expressing Cc aaor, but decreased xylitol production in the strain expressing Zm gfor. In addition, expression of Cc aaor together with the D-xylonolactone lactonase encoding the gene xylC from C. crescentus slightly increased the final concentration and initial volumetric production rate of both D-xylonate and D-xylitol. These results suggest that C. crescentus AAOR is a novel type of oxidoreductase able to convert the single aldose substrate D-xylose to both its oxidized and reduced product.

Xylose utilization in recombinant Zymomonas

DOEpatents

Kahsay, Robel Y; Qi, Min; Tao, Luan; Viitanen, Paul V; Yang, Jianjun

2013-01-07

Zymomonas expressing xylose isomerase from A. missouriensis was found to have improved xylose utilization, growth, and ethanol production when grown in media containing xylose. Xylose isomerases related to that of A. missouriensis were identified structurally through molecular phylogenetic and Profile Hidden Markov Model analyses, providing xylose isomerases that may be used to improve xylose utilization.

Organometallic oxides: Preparation, structure, and chemical and physical properties of paramagnetic ((. eta. -C sub 5 H sub 5 )NbCl(. mu. -A)) sup 3 (. mu. sub 3 -OH)(. mu. sub 3 -O) (A = Cl, OH) and other oxo-hydroxo clusters of niobium

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bottomley, F.; Keizer, P.N.; White, P.S.

Hydrolysis of Cp{prime}NbCl{sub 4} (Cp{prime} = {eta}{sup 5}-C{sub 5}H{sub 5} (Cp), {eta}-C{sub 5}H{sub 4}Me (Cp{sup 1})) in tetrahydrofuran (THF) gave a mixture of products of general formula (Cp{prime}NbL{sub 4}){sub 2}({mu}-O), where L{sub 4} is a combination of H{sub 2}O and terminal or bridging Cl that gives eight-coordinate, pentavalent, niobium. For Cp{prime} = Cp, a major constituent of the mixture is (CpNb(H{sub 2}O)Cl{sub 3}){sub 2}({mu}-O) {times} 2THF {times} 0.05Et{sub 2}O (1), the structure of which was determined by X-ray diffraction. Reduction of (Cp{prime}NbL{sub 4}){sub 2}({mu}-O) with aluminum powder gave the cluster (Cp{prime}NbCl({mu}-Cl)){sub 3}({mu}{sub 3}-OH)({mu}{sub 3}-O) (2). The structure of 2 (Cp{prime}more » = Cp) as the THF adduct was determined by X-ray diffraction. Crystal data: monoclinic; P2{sub 1}/c; a = 9.966 (1) {angstrom}, b = 12.471 (2) {angstrom}, c = 20.321 (2) {angstrom}, {beta} = 93.86 (1){degree}.« less

Cyclopentadienylniobium and -molybdenum phosphorodithioate complexes. X-ray crystal structures of CpNbCl sub 3 (S sub 2 P(OPr sup i ) sub 2 ), CpNbCl(. mu. -Cl) sub 2 Nb(S sub 2 P(OPr sup i ) sub 2 )Cp, and cis-Cp prime Mo(CO) sub 2 (S sub 2 P(OPr sup i ) sub 2 )

DOE Office of Scientific and Technical Information (OSTI.GOV)

Woodward, S.; Riaz, U.; Curtis, M.D.

1990-10-01

Reaction of CpNbCl{sub 4} (Cp = {eta}-C{sub 5}H{sub 5}) with (Pr{sup i}O){sub 2}P(S)(SH) in the presence of NEt{sub 3} yields CpNbCl{sub 3}(S{sub 2}P(S{sub 2}Pr{sup i}){sub 2}) (1). Reduction of 1 with Na/Hg affords the Nb-Nb-bonded complex CpNbCl({mu}-Cl){sub 2}Nb(S{sub 2}P(OR){sub 2})Cp (2). In refluxing toluene, (Pr{sup i}O){sub 2}P(S)(SH) with (Cp{prime}Mo(CO){sub 3}){sub 2} (Cp{prime} = {eta}-C{sub 5}H{sub 4}Me) gives cis-Cp{prime}Mo(CO){sub 2}(S{sub 2}P(OPr{sup i}){sub 2}) (3). Oxidation of 3 with I{sub 2} affords Cp{prime}MoI{sub 2}(CO)(S{sub 2}P(OPr{sup i}){sub 2}) (4). The crystal structures of 1-3 are compared. For 1, triclinic, P{bar 1}, a = 7.122 (3) {angstrom}, b = 11.365 (4) {angstrom}, c =more » 12.532 (4) {angstrom}, {alpha} = 77.38 (3){degree}, {beta} = 89.08 (3){degree}, {gamma} = 72.87 (3){degree}, V = 944.5 (8) {angstrom}{sup 3}. For 2, triclinic, P{bar 1}, a = 7.251 (3) {angstrom}, b = 12.386 (5) {angstrom}, c = 13.988 (5) {angstrom}, {alpha} = 102.66 (3){degree}, {beta} = 103.56 (3){degree}, {gamma} = 94.66 (3){degree}, V = 1180.0 (8) {angstrom}{sup 3}, Z = 2. For 3, orthorhombic, Pbca, a = 12.703 (3) {angstrom}, b = 16.707 (4) {angstrom}, c = 18.398 (4) {angstrom}, V = 3904.4 (17) {angstrom}{sup 3}, Z = 8.« less

Pentaarylcyclopentadienyl Iron, Cobalt, and Nickel Halides.

PubMed

Chakraborty, Uttam; Modl, Moritz; Mühldorf, Bernd; Bodensteiner, Michael; Demeshko, Serhiy; van Velzen, Niels J C; Scheer, Manfred; Harder, Sjoerd; Wolf, Robert

2016-03-21

The preparation of new stable half-sandwich transition metal complexes, having a bulky cyclopentadienyl ligand C5(C6H4-4-Et)5 (Cp(Ar1)) or C5(C6H4-4-nBu)5 (Cp(Ar2)), is reported. The tetrahydrofuran (THF) adduct [Cp(Ar1)Fe(μ-Br)(THF)]2 (1a) was synthesized by reacting K[Cp(Ar1)] with [FeBr2(THF)2] in THF, and its molecular structure was determined by X-ray crystallography. Complex 1a easily loses its coordinated THF molecules under vacuum to form the solvent-free complex [Cp(Ar1)Fe(μ-Br)]2 (1b). The analogous complexes [Cp(Ar1)Co(μ-Br)]2 (2), [Cp(Ar1)Ni(μ-Br)]2 (3), and [Cp(Ar2)Ni(μ-Br)]2 (4) were synthesized from CoBr2 and [NiBr2(1,2-dimethoxyethane)]. The mononuclear, low-spin cobalt(III) and nickel(III) complexes [Cp(Ar2)MI2] (5, M = Co; 6, M = Ni) were prepared by reacting the radical Cp(Ar2) with NiI2 and CoI2. The complexes were characterized by NMR and UV-vis spectroscopies and by elemental analyses. Single-crystal X-ray structure analyses revealed that the dimeric complexes 1a, 1b, and 3 have a planar M2Br2 core, whereas 2 and 4 feature a puckered M2Br2 ring.

Increasing dietary crude protein does not increase the methionine requirement in kittens.

PubMed

Strieker, M J; Morris, J G; Kass, P H; Rogers, Q R

2007-12-01

The objective of this study was to determine if the methionine (met) requirement of kittens is correlated with the concentration of dietary crude protein (CP). The study used 48 male kittens in two replications of six 4 x 4 Latin squares, each representing one concentration of met (1.5, 2.5, 3.5, 4.5, 6.0 or 9.0 g/kg diet) with four CP concentrations (150, 200, 300 and 500 g/kg diet) in 2-week periods. Cystine was present in the lowest CP diet at 5.3 g/kg diet and increased as dietary CP increased. Body weight gain, food intake, nitrogen balance and plasma amino acids, glucose, insulin, cortisol, somatomedin C, T(3) and T(4) concentrations on day 12 were measured. From breakpoint analysis of the nitrogen retention curves, the met requirement of kittens was found to be 3.1, 3.8, 3.1 and 2.4 g met/kg for the 150, 200, 300 and 500 g CP/kg diets, respectively. When met was limiting (1.5 or 2.5 g/kg diet), increasing dietary CP did not decrease, but rather increased food intake, body weight gain and nitrogen retention. Plasma met concentrations increased as dietary met increased and at 2.5-3.5 g met/kg diet were not different among kittens fed the various CP diets. Total plasma T(3) and T(4) increased significantly as dietary CP increased in kittens given the 2.5 and 4.5 g met/kg diets. Results indicate that food intake and possibly altered hormonal secretion play a role in this growth response. In conclusion, the met requirement of growing kittens, unlike omnivores and herbivores studied, was not positively correlated with the concentration of dietary CP.

Mono- and dinuclear tetraphosphabutadiene ferrate anions.

PubMed

Chakraborty, Uttam; Leitl, Julia; Mühldorf, Bernd; Bodensteiner, Michael; Pelties, Stefan; Wolf, Robert

2018-03-12

Reduction of [Cp Ar Fe(μ-Br)] 2 (1, Cp Ar = C 5 (C 6 H 4 -4-Et) 5 ) by potassium napthalenide, followed by the addition of white phosphorus, affords [K(18-c-6){Cp Ar Fe(η 4 -P 4 )}] (2, 18-c-6 = [18]crown-6), which features a planar cyclo-P 4 2- ligand. The related diiron complex [Na 2 (THF) 5 (Cp Ar Fe) 2 (μ,η 4:4 -P 4 )] (3) was obtained by reducing 1 with sodium amalgam in the presence of P 4 . Protonation of 3 affords [Na(THF) 3 ][(Cp Ar Fe) 2 (μ,η 4:4 -P 4 )(H)] (4), while the reaction of 3 with trimethylchlorosilane gives the nortricyclane compound P 7 (SiMe 3 ) 3 as the main product.

Synthesis, structural characterization and conversion of dinuclear iron-sulfur clusters containing the disulfide ligand: [Cp*Fe(μ-η2:η2-bdt)(cis-μ-η1:η1-S2)FeCp*], [Cp*Fe(μ-S(C6H4S2))(cis-μ-η1:η1-S2)FeCp*], and [{Cp*Fe(bdt)}2(trans-μ-η1:η1-S2)].

PubMed

Ji, Xiaoxiao; Tong, Peng; Yang, Dawei; Wang, Baomin; Zhao, Jinfeng; Li, Yang; Qu, Jingping

2017-03-21

The treatment of [Cp*Fe(μ-η 2 :η 4 -bdt)FeCp*] (1, Cp* = η 5 -C 5 Me 5 , bdt = benzene-1,2-dithiolate) with 1/4 equiv. of elemental sulfur (S 8 ) gave a dinuclear iron-sulfur cluster [Cp*Fe(μ-η 2 :η 2 -bdt)(cis-μ-η 1 :η 1 -S 2 )FeCp*] (2), which contains a cis-1,2-disulfide ligand. When complex 2 further interacted with 1/8 equiv. of S 8 , another sulfur atom inserted into an Fe-S bond to give a rare product [Cp*Fe(μ-S(C 6 H 4 S 2 ))(cis-μ-η 1 :η 1 -S 2 )FeCp*] (3). Unexpectedly, a trans-1,2 disulfide-bridged diiron complex [{Cp*Fe(bdt)} 2 (trans-μ-η 1 :η 1 -S 2 )] (4) was isolated from the reaction of complex 1 with 1/2 equiv. of S 8 , which represents a structural isomer of [2Fe-2S] ferredoxin-type clusters. In addition, cis-1,2-disulfide-bridged complex 3 can slowly convert into trans-1,2-disulfide-bridged complex 4 and the complex [Cp*Fe(μ-η 2 :η 2 -S 2 )(cis-μ-η 1 :η 1 -S 2 )FeCp*] (5) by self-assembly reaction at ambient temperature, which is evidenced by time-dependent 1 H NMR spectroscopy.

Single Electron Delivery to Lewis Pairs: An Avenue to Anions by Small Molecule Activation.

PubMed

Liu, Liu Leo; Cao, Levy L; Shao, Yue; Stephan, Douglas W

2017-07-26

Single electron transfer (SET) reactions are effected by the combination of a Lewis acid (e.g., E(C 6 F 5 ) 3 E = B or Al) with a small molecule substrate and decamethylferrocene (Cp* 2 Fe). Initially, the corresponding reactions of (PhS) 2 and (PhTe) 2 were shown to give the species [Cp* 2 Fe][PhSB(C 6 F 5 ) 3 ] 1 and [Cp* 2 Fe][(μ-PhS)(Al(C 6 F 5 ) 3 ) 2 ] 2 and [Cp* 2 Fe][(μ-PhTe)(Al(C 6 F 5 ) 3 ) 2 ] 3, respectively. Analogous reactions with di-tert-butyl peroxide yielded [Cp* 2 Fe][(μ-HO)(B(C 6 F 5 ) 3 ) 2 ] 4 with isobutene while with benzoyl peroxide afforded [Cp* 2 Fe][PhC(O)OE(C 6 F 5 ) 3 ] (E = B 5, Al 6). Evidence for a radical pathway was provided by the reaction of Ph 3 SnH and p-quinone afforded [Cp* 2 Fe][HB(C 6 F 5 ) 3 ] 7 and [Cp* 2 Fe] 2 [(μ-O 2 C 6 H 4 )(E(C 6 F 5 ) 3 ) 2 ] (E = B 8, Al 9). In addition, the reaction of TEMPO with Lewis acid and Cp* 2 Fe afforded [Cp* 2 Fe][(C 5 H 6 Me 4 NOE(C 6 F 5 ) 3 ] (E = B 10, Al 11). Finally, reactions with O 2 , Se, Te and S 8 gave [Cp* 2 Fe] 2 [((C 6 F 5 ) 2 Al(μ-O)Al(C 6 F 5 ) 3 ) 2 ] 2 12, [Cp* 2 Fe] 2 [((C 6 F 5 ) 2 Al(μ-Se)Al(C 6 F 5 ) 3 ) 2 ] 2 13, [Cp* 2 Fe][(μ-Te) 2 (Al(C 6 F 5 ) 2 ) 3 ] 14 and [Cp* 2 Fe] 2 [(μ-S 7 )B(C 6 F 5 ) 3 ) 2 ] 15, respectively. The mechanisms of these SET reactions are discussed, and the ramifications are considered.

Xylitol synthesis mutant of xylose-utilizing zymomonas for ethanol production

DOEpatents

Viitanen, Paul V.; Chou, Yat-Chen; McCutchen, Carol M.; Zhang, Min

2010-06-22

A strain of xylose-utilizing Zymomonas was engineered with a genetic modification to the glucose-fructose oxidoreductase gene resulting in reduced expression of GFOR enzyme activity. The engineered strain exhibits reduced production of xylitol, a detrimental by-product of xylose metabolism. It also consumes more xylose and produces more ethanol during mixed sugar fermentation under process-relevant conditions.

Global occurrence and heterogeneity of the Roseobacter-clade species Ruegeria mobilis

PubMed Central

Sonnenschein, Eva C; Nielsen, Kristian F; D'Alvise, Paul; Porsby, Cisse H; Melchiorsen, Jette; Heilmann, Jens; Kalatzis, Panos G; López-Pérez, Mario; Bunk, Boyke; Spröer, Cathrin; Middelboe, Mathias; Gram, Lone

2017-01-01

Tropodithietic acid (TDA)-producing Ruegeria mobilis strains of the Roseobacter clade have primarily been isolated from marine aquaculture and have probiotic potential due to inhibition of fish pathogens. We hypothesized that TDA producers with additional novel features are present in the oceanic environment. We isolated 42 TDA-producing R. mobilis strains during a global marine research cruise. While highly similar on the 16S ribosomal RNA gene level (99–100% identity), the strains separated into four sub-clusters in a multilocus sequence analysis. They were further differentiated to the strain level by average nucleotide identity using pairwise genome comparison. The four sub-clusters could not be associated with a specific environmental niche, however, correlated with the pattern of sub-typing using co-isolated phages, the number of prophages in the genomes and the distribution in ocean provinces. Major genomic differences within the sub-clusters include prophages and toxin-antitoxin systems. In general, the genome of R. mobilis revealed adaptation to a particle-associated life style and querying TARA ocean data confirmed that R. mobilis is more abundant in the particle-associated fraction than in the free-living fraction occurring in 40% and 6% of the samples, respectively. Our data and the TARA data, although lacking sufficient data from the polar regions, demonstrate that R. mobilis is a globally distributed marine bacterial species found primarily in the upper open oceans. It has preserved key phenotypic behaviors such as the production of TDA, but contains diverse sub-clusters, which could provide new capabilities for utilization in aquaculture. PMID:27552638

Giant Spherical Cluster with I-C140 Fullerene Topology**

PubMed Central

Heinl, Sebastian; Peresypkina, Eugenia; Sutter, Jörg; Scheer, Manfred

2015-01-01

We report on an effective cluster expansion of CuBr-linked aggregates by the increase of the steric bulk of the CpR ligand in the pentatopic molecules [CpRFe(η5-P5)]. Using [CpBIGFe(η5-P5)] (CpBIG=C5(4-nBuC6H4)5), the novel multishell aggregate [{CpBIGFe(η5:2:1:1:1:1:1-P5)}12(CuBr)92] is obtained. It shows topological analogy to the theoretically predicted I-C140 fullerene molecule. The spherical cluster was comprehensively characterized by various methods in solution and in the solid state. PMID:26411255

Association between socioeconomic status and cerebral palsy.

PubMed

Tseng, Sung-Hui; Lee, Jiun-Yih; Chou, Yi-Lin; Sheu, Mei-Ling; Lee, Yuan-Wen

2018-01-01

The present study investigated the annual prevalence of cerebral palsy (CP) among children aged <7 years in Taiwan and the association between socioeconomic status and CP prevalence. Data from the Taiwan National Health Insurance Research Database for the 2002-2008 period were used in this population-based study. Severe and total CP were defined according to catastrophic illness certificate and medical claim records, respectively. The annual CP prevalence was calculated as the number of children with CP among all children aged <7 years. From 2002 to 2008, the annual prevalence of total and severe CP ranged from 1.9 to 2.8 and from 1.1 to 1.4 per 1000 children, respectively. Boys were 30% more likely to have CP than girls [adjusted relative risk (RR) and 95% confidence interval (CI) ranged from 1.3 (1.2-1.4) to 1.4 (1.2-1.5)]. Low family income was associated with a higher CP prevalence [adjusted RR (95% CI) ranged from 5.1 (4.2-6.2) to 6.4 (5.4-7.6)]. The prevalence of CP in rural area was higher than that in urban or suburban areas. The mortality rate of severe CP ranged from 12.2-22.7 per 1000 children within the 7 years study period. The prevalence of CP in Taiwan is similar to that in Western countries. A higher prevalence of CP is associated with male sex, low income, and rural residential location. Our findings provide insights into CP epidemiology among the Chinese population.

50 CFR 679.20 - General limitations.

Code of Federal Regulations, 2014 CFR

2014-10-01

...% (ii) Trawl CP 50% 30% 20% (2) Hook-and-line CP and hook-and-line CV ≥60 ft (18.3 m) LOA 60% 40% no C...-and-line CV ≥60 ft (18.3 m) LOA 0.2 (4) Hook-and-line CP 48.7 (5) Pot CV ≥60 ft (18.3 m) LOA 8.4 (6) Pot CP 1.5 (7) AFA trawl CP 2.3 (8) Amendment 80 sector 13.4 (9) Trawl CV 22.1 (B) Incidental catch...

Isolation, characterization, and primary structure of rubredoxin from the photosynthetic bacterium, Heliobacillus mobilis

NASA Technical Reports Server (NTRS)

Lee, W. Y.; Brune, D. C.; LoBrutto, R.; Blankenship, R. E.

1995-01-01

Rubredoxin is a small nonheme iron protein that serves as an electron carrier in bacterial systems. Rubredoxin has now been isolated and characterized from the strictly anaerobic phototroph, Heliobacillus mobilis. THe molecular mass (5671.3 Da from the amino acid sequence) was confirmed and partial formylation of the N-terminal methionyl residue was established by matrix-assisted laser desorption mass spectroscopy. The complete 52-amino-acid sequence was determined by a combination of N-terminal sequencing by Edman degradation and C-terminal sequencing by a novel method using carboxypeptidase treatment in conjunction with amino acid analysis and laser desorption time of flight mass spectrometry. The molar absorption coefficient of Hc. mobilis rubredoxin at 490 nm is 6.9 mM-1 cm-1 and the midpoint redox potential at pH 8.0 is -46 mV. The EPR spectrum of the oxidized form shows resonances at g = 9.66 and 4.30 due to a high-spin ferric iron. The amino acid sequence is homologous to those of rubredoxins from other species, in particular, the gram-positive bacteria, and the phototrophic green sulfur bacteria, and the evolutionary implications of this are discussed.

Heterometallic niobium complexes containing the {open_quotes}CpNb{close_quotes} unit. X-ray crystal structures of CpNbCl{sub 2}({mu}-SEt){sub 2}NiCp and CpNb(PhCCPh)({mu}-SPr{sup 1}){sub 2}Mo(CO){sub 4}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Woodward, S.; Curtis, M.D.; Rheingold, A.L.

1992-06-01

Cp{sub 2}Nb{sub 2}Cl{sub 2}({mu}-Cl{sub 2})(CO){sub 4} reacts with Cp{sub 2}Ni{sub 2}({mu}-SEt){sub 2} to yield paramagnetic CpNbCl{sub 2}({mu}-SEt){sub 2}NiCp: (g) = 2.004, A = 129 G; space group = P2{sub 1}/c,a = 7.466 (1) {Angstrom}, b = 28.427 (5) {Angstrom}, c = 8.620 (2) {Angstrom}, {beta} = 104.81 (1){degree}. CpNb(PhCCPh)({mu}-SPr{sup i}){sub 2}Mo(CO){sub 4} is synthesized by the addition of LiSPr{sup i} to CpNbCl{sub 2}PhCCPh resulting in formation of CpNb(SPr{sup i}){sub 2}(PhCCPh) followed by the reaction of the thiolate complex with Mo(MeCN){sub 3}(CO){sub 3} and CO (1 equiv). The crystal structure for CpNb(PhCCPh)({mu}-SPr{sup i}){sub 2}Mo(CO){sub 4} is reported and EHMO calculations ofmore » the bonding in CpNbCl{sub 2}({mu}-SEt{sub 2})NiCp were discussed. 27 refs., 5 figs., 5 tabs.« less

Chemistry of group 9 dimetallaborane analogues of octaborane(12).

PubMed

Barik, Subrat Kumar; Roy, Dipak Kumar; Ghosh, Sundargopal

2015-01-14

We report the synthesis, isolation and structural characterization of several moderately air stable nido-metallaboranes that represent boron rich open cage systems. The reaction of [Cp*CoCl]2, (Cp* = η(5)-C5Me5), with [BH3·thf] in toluene at ice cold temperature, followed by thermolysis in boiling toluene produced [(Cp*Co)B9H13], 1 [(Cp*Co)2B8H12], 2 and [(Cp*Co)2B6H10] 3. Building upon our earlier reactivity studies on rhodaboranes, we continue to explore the reactivity of dicobalt analogues of octaborane(12) cluster 3 with [Fe2(CO)9] and [Ru3(CO)12] at ambient conditions that yielded novel fused clusters [Fe2(CO)6(Cp*Co)2B6H10], 4 and [Ru4(CO)11(Cp*Co)2B3H3], 5 respectively. In an attempt to synthesize a heterometallic metallaborane compound we performed the reaction of [(Cp*Rh)2B6H10], 6 with [Cp*IrH4] that yielded a Ir-Ir double bonded compound [(Cp*Ir)2H3][B(OH)4], 7. All the new compounds have been characterized by IR, (1)H, (11)B, (13)C NMR spectroscopy, and the molecular structures were unambiguously established by X-ray diffraction analysis.

Mechanical mandible competence in rats with nutritional growth retardation.

PubMed

Lezón, Christian Esteban; Pintos, Patricia Mabel; Bozzini, Clarisa; Romero, Alan Agüero; Casavalle, Patricia; Friedman, Silvia María; Boyer, Patricia Mónica

2017-08-01

In order to provide a better understanding of the sympathetic nervous system as a negative regulator of bone status, the aim of the study was to establish the biomechanical mandible response to different doses of a β-adrenergic antagonist such as propranolol (P) in a stress-induced food restriction model of growth retardation. Rats were assigned to eight groups: Control (C), C+P3.5 (CP3.5), C+P7 (CP7), C+P14 (CP14), NGR, NGR+P3.5 (NGRP3.5), NGR+P7 (NGRP7) and NGR+P14 (NGRP14). C, CP3.5, CP7 and CP14 rats were freely fed with the standard diet. NGR, NGRP3.5, NGRP7 and NGRP14 rats received, for 4 weeks (W4), 80% of the amount of controls food consumed. Propranolol 3.5, 7 and 14mg/kg/day was injected ip 5days per week in CP3.5 and NGRP3.5, CP7 and NGRP7, CP14 and NGRP14, respectively. At W4, zoometry, mandible morphometry, static histomorphometric and biomechanical competence were performed. A dose of Propranolol 7mg/kg/day induced interradicular bone volume accretion reaching a mandible stiffness according to chronological age. These findings evidenced that sympathetic nervous system activity is a negative regulator of mandible mechanical competence in the nutritional growth retardation model. Propranolol 7mg/kg/day, under the regimen usage, seems to be appropriate to blockade SNS activity on mandible mechanical performance in NGR rats, probably associated to an effect on bone mechanostat system ability to detect disuse mode as an error. Copyright © 2017 Elsevier Ltd. All rights reserved.

Giant Spherical Cluster with I-C140 Fullerene Topology.

PubMed

Heinl, Sebastian; Peresypkina, Eugenia; Sutter, Jörg; Scheer, Manfred

2015-11-02

We report on an effective cluster expansion of CuBr-linked aggregates by the increase of the steric bulk of the Cp(R) ligand in the pentatopic molecules [Cp(R)Fe(η(5)-P5)]. Using [Cp(BIG)Fe(η(5)-P5)] (Cp(BIG)=C5(4-nBuC6H4)5), the novel multishell aggregate [{Cp(BIG)Fe(η(5:2:1:1:1:1:1)-P5)}12(CuBr)92] is obtained. It shows topological analogy to the theoretically predicted I-C140 fullerene molecule. The spherical cluster was comprehensively characterized by various methods in solution and in the solid state. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Association between socioeconomic status and cerebral palsy

PubMed Central

Tseng, Sung-Hui; Lee, Jiun-Yih; Chou, Yi-Lin; Sheu, Mei-Ling

2018-01-01

Background The present study investigated the annual prevalence of cerebral palsy (CP) among children aged <7 years in Taiwan and the association between socioeconomic status and CP prevalence. Methods Data from the Taiwan National Health Insurance Research Database for the 2002−2008 period were used in this population-based study. Severe and total CP were defined according to catastrophic illness certificate and medical claim records, respectively. The annual CP prevalence was calculated as the number of children with CP among all children aged <7 years. Results From 2002 to 2008, the annual prevalence of total and severe CP ranged from 1.9 to 2.8 and from 1.1 to 1.4 per 1000 children, respectively. Boys were 30% more likely to have CP than girls [adjusted relative risk (RR) and 95% confidence interval (CI) ranged from 1.3 (1.2−1.4) to 1.4 (1.2−1.5)]. Low family income was associated with a higher CP prevalence [adjusted RR (95% CI) ranged from 5.1 (4.2−6.2) to 6.4 (5.4−7.6)]. The prevalence of CP in rural area was higher than that in urban or suburban areas. The mortality rate of severe CP ranged from 12.2−22.7 per 1000 children within the 7 years study period. Conclusions The prevalence of CP in Taiwan is similar to that in Western countries. A higher prevalence of CP is associated with male sex, low income, and rural residential location. Our findings provide insights into CP epidemiology among the Chinese population. PMID:29364952

Unexpected Reactivity of [(η(5) -1,2,4-tBu3 C5 H2 )Ni(η(3) -P3 )] towards Main Group Nucleophiles and by Reduction.

PubMed

Mädl, Eric; Balázs, Gábor; Peresypkina, Eugenia V; Scheer, Manfred

2016-06-27

The reduction of [Cp'''Ni(η(3) -P3 )] (1; Cp'''=η(5) -1,2,4-tBu3 C5 H2 ) with potassium produces the complex anion [(Cp'''Ni)2 (μ,η(2:2) -P8 )](2-) (2), which contains a realgar-like P8 unit. The anionic triple-decker sandwich complex [(Cp'''Ni)2 (μ,η(3:3) -P3 )](-) (3) with a cyclo-P3 middle deck is obtained when 1 is treated with NaNH2 as a nucleophile. Na[3] can subsequently be oxidized with AgOTf to the neutral triple-decker complex [(Cp'''Ni)2 (μ,η(3:3) -P3 )] (4). In contrast, 1 reacts with LiPPh2 to give the anionic compound [(Cp'''Ni)2 (μ,η(2:2) -P6 PPh2 )](-) (5), a complex containing a bicyclic P7 fragment capped by two Cp'''Ni units. Protonation of Li[5] with HBF4 leads to the neutral complex [(Cp'''Ni)2 (μ,η(2:2) -(HP6 PPh2 )] (6). Adding LiNMe2 to 1 results in [Cp'''Ni(η(2) -P3 NMe2 )](-) (7) becoming accessible, a complex which forms as a result of nucleophilic attack at the cyclo-P3 ring of 1. The complexes K2 [2], Na[3], 4, 6, and Li[7] were fully characterized and their structures determined by single-crystal X-ray diffraction. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The Ruthenostannylene Complex [Cp*(IXy)H2 Ru-Sn-Trip]: Providing Access to Unusual Ru-Sn Bonded Stanna-imine, Stannene, and Ketenylstannyl Complexes.

PubMed

Liu, Hsueh-Ju; Ziegler, Micah S; Tilley, T Don

2015-05-26

Reactivity studies of the thermally stable ruthenostannylene complex [Cp*(IXy)(H)2 Ru-Sn-Trip] (1; IXy=1,3-bis(2,6-dimethylphenyl)imidazol-2-ylidene; Cp*=η(5) -C5 Me5 ; Trip=2,4,6-iPr3 C6 H2 ) with a variety of organic substrates are described. Complex 1 reacts with benzoin and an α,β-unsaturated ketone to undergo [1+4] cycloaddition reactions and afford [Cp*(IXy)(H)2 RuSn(κ(2) -O,O-OCPhCPhO)Trip] (2) and [Cp*(IXy)(H)2 RuSn(κ(2) -O,C-OCPhCHCHPh)Trip] (3), respectively. The reaction of 1 with ethyl diazoacetate resulted in a tin-substituted ketene complex [Cp*(IXy)(H)2 RuSn(OC2 H5 )(CHCO)Trip] (4), which is most likely a decomposition product from the putative ruthenium-substituted stannene complex. The isolation of a ruthenium-substituted stannene [Cp*(IXy)(H)2 RuSn(=Flu)Trip] (5) and stanna-imine [Cp*(IXy)(H)2 RuSn(κ(2) -N,O-NSO2 C6 H4 Me)Trip] (6) complexes was achieved by treatment of 1 with 9-diazofluorene and tosyl azide, respectively. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Metabolic characterization and transformation of the non-dairy Lactococcus lactis strain KF147, for production of ethanol from xylose.

PubMed

Petersen, Kia Vest; Liu, Jianming; Chen, Jun; Martinussen, Jan; Jensen, Peter Ruhdal; Solem, Christian

2017-08-01

The non-dairy lactic acid bacterium Lactococcus lactis KF147 can utilize xylose as the sole energy source. To assess whether KF147 could serve as a platform organism for converting second generation sugars into useful chemicals, the authors characterized growth and product formation for KF147 when grown on xylose. In a defined medium KF147 was found to co-metabolize xylose and arginine, resulting in bi-phasic growth. Especially at low xylose concentrations, arginine significantly improved growth rate. To facilitate further studies of the xylose metabolism, the authors eliminated arginine catabolism by deleting the arcA gene encoding the arginine deiminase. The fermentation product profile suggested two routes for xylose degradation, the phosphoketolase pathway and the pentose phosphate pathway. Inactivation of the phosphoketolase pathway redirected the entire flux through the pentose phosphate pathway whereas over-expression of phosphoketolase increased the flux through the phosphoketolase pathway. In general, significant amounts of the mixed-acid products, including lactate, formate, acetate and ethanol, were formed irrespective of xylose concentrations. To demonstrate the potential of KF147 for converting xylose into useful chemicals the authors chose to redirect metabolism towards ethanol production. A synthetic promoter library was used to drive the expression of codon-optimized versions of the Zymomonas mobilis genes encoding pyruvate decarboxylase and alcohol dehydrogenase, and the outcome was a strain producing ethanol as the sole fermentation product with a high yield corresponding to 83% of the theoretical maximum. The results clearly indicate the great potential of using the more metabolically diverse non-dairy L. lactis strains for bio-production based on xylose containing feedstocks. Copyright © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Studying the rapid bioconversion of lignocellulosic sugars into ethanol using high cell density fermentations with cell recycle

PubMed Central

2014-01-01

Background The Rapid Bioconversion with Integrated recycle Technology (RaBIT) process reduces capital costs, processing times, and biocatalyst cost for biochemical conversion of cellulosic biomass to biofuels by reducing total bioprocessing time (enzymatic hydrolysis plus fermentation) to 48 h, increasing biofuel productivity (g/L/h) twofold, and recycling biocatalysts (enzymes and microbes) to the next cycle. To achieve these results, RaBIT utilizes 24-h high cell density fermentations along with cell recycling to solve the slow/incomplete xylose fermentation issue, which is critical for lignocellulosic biofuel fermentations. Previous studies utilizing similar fermentation conditions showed a decrease in xylose consumption when recycling cells into the next fermentation cycle. Eliminating this decrease is critical for RaBIT process effectiveness for high cycle counts. Results Nine different engineered microbial strains (including Saccharomyces cerevisiae strains, Scheffersomyces (Pichia) stipitis strains, Zymomonas mobilis 8b, and Escherichia coli KO11) were tested under RaBIT platform fermentations to determine their suitability for this platform. Fermentation conditions were then optimized for S. cerevisiae GLBRCY128. Three different nutrient sources (corn steep liquor, yeast extract, and wheat germ) were evaluated to improve xylose consumption by recycled cells. Capacitance readings were used to accurately measure viable cell mass profiles over five cycles. Conclusion The results showed that not all strains are capable of effectively performing the RaBIT process. Acceptable performance is largely correlated to the specific xylose consumption rate. Corn steep liquor was found to reduce the deleterious impacts of cell recycle and improve specific xylose consumption rates. The viable cell mass profiles indicated that reduction in specific xylose consumption rate, not a drop in viable cell mass, was the main cause for decreasing xylose consumption. PMID:24847379

Synthesis, spectral, and structural studies of porphyrins having sterically hindered [η(5)-CpCo(η(4)-C4Ph4)] cobalt sandwich units at the meso positions.

PubMed

Keshav, Karunesh; Kumar, Dheeraj; Elias, Anil J

2013-11-04

Synthesis, spectral, and structural studies of the first examples of porphyrins substituted at the meso positions with sterically hindered η(5)-CpCo(η(4)-C4Ph4) cobalt sandwich units are described. The novel dipyrromethane derived cobalt sandwich compound {η(5)-[(C4H4N)2CH]C5H4}Co(η(4)-C4Ph4) 1, as well as its parent aldehyde, η(5)-[C5H4(CHO)]Co(η(4)-C4Ph4), were used in the synthesis of porphyrins having one or two η(5)-CpCo(η(4)-C4Ph4) groups at their meso positions. 1,9-Diformyldipyrromethane derived η(5)-CpCo(η(4)-C4Ph4) 2 was synthesized using dipyrromethane 1 under Vilsmeier conditions. A reaction of 2 with unsubstituted dipyrromethane under basic conditions in the presence of Pd(C6H5CN)2Cl2 yielded an A-type palladium coordinated porphyrin 3 [where A = η(5)-CpCo(η(4)-C4Ph4)]. A similar reaction of 2 with meso aryl and ferrocenyl-substituted dipyrromethanes yielded trans-AB type palladium coordinated porphyrins 4-6 [where A = η(5)-CpCo(η(4)-C4Ph4) and B = 4-tert-butylphenyl 4, ferrocenyl 5, and pentafluorophenyl 6]. Reactions of 2 with 5-ferrocenyl dipyrromethane under the same reaction conditions in the presence of Ni(acac)2 and Zn(OAc)2 gave the trimetallic nickel(II) and zinc(II) complexed trans-AB type porphyrins 7 and 8 having both cobalt and iron sandwich units at the meso positions. Crystal structure of the Pd(II) porphyrin 5 and nickel(II) porphyrin 7 showed nonplanar structures having distinct ruffle type distortion of the porphyrin ring. Demetalation of the zinc(II) trans-AB type porphyrin 8 in the presence of trifluoroacetic acid gave the metal free base porphyrin 9. Reactions of the cobalt sandwich aldehyde [(η(5)-C5H4(CHO)]Co(η(4)-C4Ph4) with sterically hindered dipyrromethane derivatives under acid-catalyzed condensation reactions gave trans-A2B2 type porphyrins [where A = η(5)-CpCo(η(4)-C4Ph4) and B = pentafluorophenyl, 10 mesityl 11]. In contrast, reactions of [η(5)-C5H4(CHO)]Co(η(4)-C4Ph4) with sterically unhindered meso-4-tert-butylphenyl dipyrromethane resulted in both AB3 12 and cis-A2B2 13 type porphyrins [where A = η(5)-CpCo(η(4)-C4Ph4) and B = (4-tert-butylphenyl] as a result of scrambling. The new porphyrin derivatives have been structurally characterized, and their spectral and electrochemical features were determined.

FIB-4 index for assessing the prognosis of hepatocellular carcinoma in patients with Child-Pugh class A liver function.

PubMed

Ito, Takanori; Kumada, Takashi; Toyoda, Hidenori; Tada, Toshifumi

2015-07-01

We evaluated the prognosis of hepatocellular carcinoma (HCC) patients with Child-Pugh (C-P) class A based on FIB-4 index, which is a liver fibrosis marker. A total of 915 HCC patients with C-P class A were investigated. We assessed the prognosis using FIB-4 index, and factors associated with survival rates were analyzed in these patients. When patients were categorized according to FIB-4 index as <2.0 (n = 93), ≥ 2.0 and <4.0 (n = 311), and ≥ 4.0 (n = 511), survival rates at 5 years were 70.5% [95% confidence interval (CI) 59.0-79.9], 56.4% (95% CI 50.1-62.5), and 47.1% (95% CI 42.2-52.1), respectively. Patients with FIB-4 index <2.0 had a higher survival rate than the other groups (≥ 4.0 vs ≥ 2.0 and <4.0, p = 0.010; ≥ 2.0 and <4.0 vs <2.0, p = 0.028). We were able to predict prognosis in patients with C-P score 5 by FIB-4 index, but survival rate did not significantly differ in patients with C-P score 6. Multivariate analysis identified C-P score, FIB-4 index [≥ 2.0 and <4.0; hazard ratios (HRs) 1.638 (95% CI 1.084-2.474); p = 0.019/≥ 4.0; HR 1.828 (95% CI 1.217-2.744); p = 0.004], Lens culinaris agglutinin-reactive α-fetoprotein, tumor size, number, vascular invasion, antiviral therapy, and hepatectomy as independent predictive factors for survival. The FIB-4 index is useful for assessing prognosis in HCC patients with C-P class A, especially those with C-P score 5.

Excretion, metabolism, and pharmacokinetics of 1-(8-(2-chlorophenyl)-9-(4-chlorophenyl)-9H-purin-6-yl)-4-(ethylamino)piperidine-4-carboxamide, a selective cannabinoid receptor antagonist, in healthy male volunteers.

PubMed

Miao, Zhuang; Sun, Hao; Liras, Jennifer; Prakash, Chandra

2012-03-01

The disposition of 1-(8-(2-chlorophenyl)-9-(4-chlorophenyl)-9H- purin-6-yl)-4-(ethylamino)-piperidine-4-carboxamide (CP-945,598), an orally active antagonist of the cannabinoid CB1 receptor, was studied after a single 25-mg oral dose of [(14)C]CP-945,598 to healthy human subjects. Serial blood samples and complete urine and feces were collected up to 672 h after dose. The mean total recovery of radioactivity was 60.1 ± 12.8 from the urine and feces, with the majority of the dose excreted in the feces. The absorption of CP-945,598 in humans was slow with T(max) at 6 h. Less than 2% of the dose was recovered as unchanged drug in the combined excreta, suggesting that CP-945,598 is extensively metabolized. The primary metabolic pathway of CP-945,598 involved N-de-ethylation to form an N-desethyl metabolite (M1), which was then subsequently metabolized by amide hydrolysis (M2), N-hydroxylation (M3), piperidine ring hydroxylation (M6), and ribose conjugation (M9). M3 was further metabolized to oxime (M4) and keto (M5) metabolites. M1, M4, and M5 were the major circulating metabolites, with AUC((0-48)) values 4.7-, 1.5-, and 1.1-fold greater than that of CP-945,598. M1, M2, and M9 accounted for 5.6, 33.6, and 6.30% of the dose, respectively, in excreta. The results from in vitro experiments with recombinant isoforms suggested that the oxidative metabolism of CP-945,598 to M1 is catalyzed primarily by CYP3A4/3A5. The molecular docking study showed that the N-ethyl moiety of CP-945,598 can access to the heme iron-oxo of CYP3A4 in an energetically favored orientation. Together, these data suggest that CP-945,598 is well absorbed and eliminated largely by CYP3A4/3A5-catalyzed metabolism.

Metabolic engineering of a tyrosine-overproducing yeast platform using targeted metabolomics.

PubMed

Gold, Nicholas D; Gowen, Christopher M; Lussier, Francois-Xavier; Cautha, Sarat C; Mahadevan, Radhakrishnan; Martin, Vincent J J

2015-05-28

L-tyrosine is a common precursor for a wide range of valuable secondary metabolites, including benzylisoquinoline alkaloids (BIAs) and many polyketides. An industrially tractable yeast strain optimized for production of L-tyrosine could serve as a platform for the development of BIA and polyketide cell factories. This study applied a targeted metabolomics approach to evaluate metabolic engineering strategies to increase the availability of intracellular L-tyrosine in the yeast Saccharomyces cerevisiae CEN.PK. Our engineering strategies combined localized pathway engineering with global engineering of central metabolism, facilitated by genome-scale steady-state modelling. Addition of a tyrosine feedback resistant version of 3-deoxy-D-arabino-heptulosonate-7-phosphate synthase Aro4 from S. cerevisiae was combined with overexpression of either a tyrosine feedback resistant yeast chorismate mutase Aro7, the native pentafunctional arom protein Aro1, native prephenate dehydrogenase Tyr1 or cyclohexadienyl dehydrogenase TyrC from Zymomonas mobilis. Loss of aromatic carbon was limited by eliminating phenylpyruvate decarboxylase Aro10. The TAL gene from Rhodobacter sphaeroides was used to produce coumarate as a simple test case of a heterologous by-product of tyrosine. Additionally, multiple strategies for engineering global metabolism to promote tyrosine production were evaluated using metabolic modelling. The T21E mutant of pyruvate kinase Cdc19 was hypothesized to slow the conversion of phosphoenolpyruvate to pyruvate and accumulate the former as precursor to the shikimate pathway. The ZWF1 gene coding for glucose-6-phosphate dehydrogenase was deleted to create an NADPH deficiency designed to force the cell to couple its growth to tyrosine production via overexpressed NADP(+)-dependent prephenate dehydrogenase Tyr1. Our engineered Zwf1(-) strain expressing TYRC ARO4(FBR) and grown in the presence of methionine achieved an intracellular L-tyrosine accumulation up to 520 μmol/g DCW or 192 mM in the cytosol, but sustained flux through this pathway was found to depend on the complete elimination of feedback inhibition and degradation pathways. Our targeted metabolomics approach confirmed a likely regulatory site at DAHP synthase and identified another possible cofactor limitation at prephenate dehydrogenase. Additionally, the genome-scale metabolic model identified design strategies that have the potential to improve availability of erythrose 4-phosphate for DAHP synthase and cofactor availability for prephenate dehydrogenase. We evaluated these strategies and provide recommendations for further improvement of aromatic amino acid biosynthesis in S. cerevisiae.

Ruthenium-Catalyzed Cycloaddition of 1-Haloalkynes with Nitrile Oxides and Organic Azides; Synthesis of 4-Halo Isoxazoles and 5-Halo Triazoles

PubMed Central

Oakdale, James S.; Sit, Rakesh K.

2015-01-01

(Cyclopentadienyl)(cyclooctadiene) ruthenium(II) chloride [CpRuCl(cod)] catalyzes the reaction between nitrile oxides and electronically deficient 1-choro-, 1-bromo- and 1-iodoalkynes leading to 4-haloisoxazoles. Organic azides are also suitable 1,3-dipoles, resulting in 5-halo-1,2,3-triazoles. These air tolerant reactions can be performed at room temperature with 1.25 equiv of the respective 1,3-dipole relative to the alkyne component. Reactive 1-haloalkynes include propiolic amides, esters, ketones and phosphonates. Post-functionalization of the halogenated azole products can be accomplished using palladium-catalyzed cross-coupling reactions as well as via manipulation of reactive amide groups. The lack of catalysis observed with Cp*RuCl(cod) is attributed to steric demands of the Cp* (η5-C5Me5) ligand in comparison to the parent Cp (η5-C5H5). This hypothesis is supported by the poor reactivity of (η5-C5Me4CF3)RuCl(cod), which serves as a an isosteric mimic of Cp* and as an isoelectronic analog of Cp. PMID:25059647

Reduction of [Cp*Sb]4 with Subvalent Main-Group Metal Reductants: Syntheses and Structures of [(L1 Mg)4 (Sb4 )] and [(L2 Ga)2 (Sb4 )] Containing Edge-Missing Sb4 Units.

PubMed

Ganesamoorthy, Chelladurai; Krüger, Julia; Wölper, Christoph; Nizovtsev, Anton S; Schulz, Stephan

2017-02-16

[Cp*Sb] 4 (Cp*=C 5 Me 5 ) reacts with [L 1 Mg] 2 and L 2 Ga with formation of [(L 1 Mg) 4 (μ 4 ,η 1:2:2:2 -Sb 4 )] (L 1 =iPr 2 NC[N(2,6-iPr 2 C 6 H 3 )] 2 , 1) and [(L 2 Ga) 2 (μ,η 2:2 -Sb 4 )] (L 2 =HC[C(Me)N(2,6-iPr 2 C 6 H 3 )] 2 , 2). The cleavage of the Sb-Sb and Sb-C bonds in [Cp*Sb] 4 are the crucial steps in both reactions. The formation of 1 occurred by elimination of the Cp* anion and formation of Cp*MgL 1 , while 2 was formed by reductive elimination of Cp* 2 and oxidative addition of L 2 Ga to the Sb 4 unit. 1 and 2 were characterized by heteronuclear NMR spectroscopy and single-crystal X-ray diffraction, and their bonding situation was studied by quantum chemical calculations. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

50 CFR 679.20 - General limitations.

Code of Federal Regulations, 2012 CFR

2012-10-01

... season (1) Trawl 60% 20% 20% (i) Trawl CV 70% 10% 20% (ii) Trawl CP 50% 30% 20% (2) Hook-and-line CP and...-line CP 48.7 (5) Pot CV ≥60 ft (18.3 m) LOA 8.4 (6) Pot CP 1.5 (7) AFA trawl CP 2.3 (8) Amendment 80...) Trawl CV 74 % 11 % 15 % (ii) Trawl CP 75 % 25 % 0 % (2) Hook-and-line CP, hook-and-line CV ≥60 ft (18.3...

50 CFR 679.20 - General limitations.

Code of Federal Regulations, 2013 CFR

2013-10-01

... season (1) Trawl 60% 20% 20% (i) Trawl CV 70% 10% 20% (ii) Trawl CP 50% 30% 20% (2) Hook-and-line CP and...-line CP 48.7 (5) Pot CV ≥60 ft (18.3 m) LOA 8.4 (6) Pot CP 1.5 (7) AFA trawl CP 2.3 (8) Amendment 80...) Trawl CV 74 % 11 % 15 % (ii) Trawl CP 75 % 25 % 0 % (2) Hook-and-line CP, hook-and-line CV ≥60 ft (18.3...

Design and Synthesis of a Biocompatible 1D Coordination Polymer as Anti-Breast Cancer Drug Carrier, 5-Fu: In Vitro and in Vivo Studies.

PubMed

Rezaei, Mahsa; Abbasi, Alireza; Dinarvand, Rassoul; Jeddi-Tehrani, Mahmood; Janczak, Jan

2018-05-17

Designable coordination polymers with suitable chemical diversities and biocompatible structures have been proposed as a promising class of vehicles for drug delivery systems. Here, we hydrothermally synthesized a novel one-dimensional (1D) coordination polymer, [Zn(H 2 O) 6 K 2 (H 2 BTC) 2 (H 2 O) 4 ](H 2 BTC) 2 ·2H 2 O, where H 3 BTC = benzene-1,3,5-tricarboxylic acid (trimesic acid), cp.1. As the hydrogen bonds stabilized 1D chains in three dimensions, the cp.1 could be a good candidate for delivering small-molecule chemotherapeutics such as 5-fluorouracil (5-Fu). The synthesized cp.1 showed a remarkable 5-Fu loading of 66% with encapsulation efficiency of 98% and almost complete release process. The 5-Fu-loaded cp.1 displayed a time-dependent cytotoxicity effect against breast cancer cell lines MCF-7 and 4T1. The cellular uptake of cp.1 particles was investigated via confocal laser scanning microscopy using fluorescein isothiocyanate and LysoTracker Red staining. Furthermore, the in vivo antitumor impact of 5-Fu-loaded cp.1 was studied on 4T1 breast cancer BALB/c mice model. The intratumor treatment of 5-Fu-loaded cp.1 demonstrated beneficial antitumor efficacy by postponing tumor growth. These results suggest that the 5-Fu-loaded cp.1 microparticles with a great locoregional delivery can be efficient anticancer drug carriers for further clinical treatments.

Anionic Hosts for the Incorporation of Cationic Guests

PubMed Central

Peresypkina, Eugenia; Heindl, Claudia; Virovets, Alexander; Brake, Helena; Mädl, Eric

2018-01-01

Abstract Pentaphosphaferrocene [Cp*Fe(η5‐P5)] (1 a) represents an excellent building block for the template‐directed synthesis of spherical supramolecules. Here, the self‐assembly of 1 a with CuI and CuII halides in the presence of the template complexes [FeCp2][PF6], [CoCp2][PF6] and [CoCp2] is reported, testifying to the redox behavior of the formed supramolecules. The oxidation or reduction capacity of these reactive complexes does not inhibit their template impact and, for the first time, the cationic metallocene [CoCp2]+ is enclosed in unprecedented anionic organometallic hosts. Furthermore, the large variety of structural motifs, as icosahedral, trigonal antiprismatic, cuboidal and tetragonal antiprismatic arrangements of 1 a units are realized in the supramolecules [FeCp2]@[{1 a}12(CuBr)17.3] (3), [CoCp2]+ 3{[CoCp2]+@[{1 a}8Cu24.25Br28.25(CH3CN)6]4−} (4), {[Cp2Co]+@[{1 a}8(CuI)28 (CH3CN)9.8]}{[Cp2Co]+@[{1 a)}8Cu24.4I26.4(CH3CN)8]2−} (5), and [{1 a}3{(1 a)2NH}3Cu16I10(CH3CN)7] (6), respectively. PMID:29236336

Variation in ruminal in situ degradation of crude protein and starch from maize grains compared to in vitro gas production kinetics and physical and chemical characteristics.

PubMed

Seifried, Natascha; Steingaß, Herbert; Schipprack, Wolfgang; Rodehutscord, Markus

2016-10-01

The objectives of this study were (1) to evaluate in situ ruminal dry matter (DM), crude protein (CP) and starch degradation characteristics and in vitro gas production (GP) kinetics using a set of 20 different maize grain genotypes and (2) to predict the effective degradation (ED) of CP and starch from chemical and physical characteristics alone or in combination with in vitro GP measurements. Maize grains were characterised by different chemical and physical characteristics. Ruminal in situ degradation was measured in three lactating Jersey cows. Ground grains (sieve size: 2 mm) were incubated in bags for 1, 2, 4, 8, 16, 24, 48 and 72 h. Bag residues were analysed for CP and starch content. Degradation kinetics was determined and the ED of DM, CP and starch calculated using a ruminal passage rate of 5%/h and 8%/h. The GP of the grains (sieve size: 1 mm) was recorded after 2, 4, 6, 8, 12, 24, 48 and 72 h incubation in buffered rumen fluid and fitted to an exponential equation to determine GP kinetics. Correlations and stepwise multiple linear regressions were evaluated for the prediction of ED calculated for a passage rate of 5%/h (ED5) for CP (EDCP5) and starch (EDST5). The in situ parameters and ED5 varied widely between genotypes with average values (±SD) of 64% ± 4.2, 62% ± 4.1 and 65% ± 5.2 for ED5 of DM, EDCP5 and EDST5 and were on average 10 percentage points lower for a passage rate of 8%/h. Degradation rates varied between 4.8%/h and 7.4%/h, 4.1%/h and 6.5%/h and 5.3%/h and 8.9%/h for DM, CP and starch, respectively. These rates were in the same range as GP rates (6.0-8.3%/h). The EDCP5 and EDST5 were related to CP concentration and could be evaluated in detail using CP fractions and specific amino acids. In vitro GP measurements and GP rates correlated well with EDCP5 and EDST5 and predicted EDCP5 and EDST5 in combination with the chemical characteristics of the samples. Equations can be used to obtain quick and cost effective information on ruminal degradation of CP and starch from maize grains.

Effect of supplementing rumen-protected methionine on production and nitrogen excretion in lactating dairy cows.

PubMed

Broderick, G A; Stevenson, M J; Patton, R A; Lobos, N E; Olmos Colmenero, J J

2008-03-01

Two 4 x 4 Latin square trials (4-wk periods; 16 wk total) were conducted to see whether supplementing rumen-protected Met (RPM; fed as Mepron) would allow feeding less crude protein (CP), thereby reducing urinary N excretion, but without losing production. In trial 1, 24 Holsteins were fed 4 diets as total mixed rations containing [dry matter (DM) basis]: 18.6% CP and 0 g of RPM/d; 17.3% CP and 5 g of RPM/d; 16.1% CP and 10 g of RPM/d; or 14.8% CP and 15 g of RPM/d. Dietary CP was reduced by replacing soybean meal with high-moisture shelled corn. All diets contained 21% alfalfa silage, 28% corn silage, 4.5% roasted soybeans, 5.8% soyhulls, 0.6% sodium bicarbonate, 0.5% vitamins and minerals, and 27% neutral detergent fiber. There was no effect of diet on intake, weight gain, or yields of protein, lactose, and solids-not-fat. However, production was greater at 17.3% CP plus RPM and 16.1% CP plus RPM than on the other 2 diets. Apparent N efficiency (milk N:N intake) was greatest on the lowest CP diet containing the most RPM. Linear reductions in milk urea N and urinary N excretion were observed with lower dietary CP. In trial 2, 32 Holsteins were fed 4 diets as total mixed rations, formulated from ingredients used in trial 1 and containing 16.1 or 17.3% CP with 0 or 10 g of RPM/d. On average, cows were calculated to be in negative N balance on all diets because of lower than expected DM intake. There was no effect of RPM supplementation on any production trait. However, higher CP gave small increases in yields of milk, protein, and solids-not-fat and tended to increase DM intake and lactose yield. Apparent N efficiency was greater, and milk urea nitrogen was lower, on 16.1% CP. In trial 1, feeding lower CP diets supplemented with RPM resulted in improved N efficiency and reduced urinary N excretion. However, in trial 2, reducing dietary CP from 17.3 to 16.1% reduced milk secretion, an effect that was not reversed by RPM supplementation at low DM intakes when cows were apparently mobilizing body protein.

The use of functionalized zirconocenes as precursors to silica-supported zirconocene olefin polymerization catalysts

NASA Astrophysics Data System (ADS)

Cheng, Xu

2001-07-01

Me3Si substituents adjacent to Cp2MCl2 (M = Ti, Zr, Hf) are converted to BrMe2Si groups using BBr 3. The high reactivity of the Si-Br bonds toward nucleophiles such as water suggested that these substituents could react with hydroxylated silica surfaces, immobilizing the metallocenes. This dissertation concerns the syntheses of electrophile-functionalized zirconocene dihalide complexes and their use as precursors to silica-supported metallocene olefin polymerization catalysts. First we extended the metallocene "functionalization" chemistry to obtain substituents bearing more than one electrophilic bond. (Me3Sn) 2C5H4 combined with CpZrCl3 in toluene to afford (eta5-Me3Sn-C5H4)CpZrCl 2 (A). Reactions of A with electrophiles (E-X = Cl2B-Cl, I-Cl, and I-I) afforded (eta5-XMe 2Sn-C5H4)CpZrCl2 (and E-Me) cleanly. The reaction of A with BBr3 afforded either (eta5-BrMe2Sn-C5H4)CpZrBr2 (25 °C, 10 min) or (eta5-Br2MeSn-C5H 4)CpZrBr2 (25 °C, 15 h). Ph2MeSi-C5H 4Li combined with ZrCl4•2THF to afford (eta 5-Ph2MeSi-C5H4)2ZrCl 2 (B). The reaction of B with BCl3 led to incomplete cleavage of the Ph-Si bonds, however treatment of B with BBr3 afforded (eta5-Br2MeSi-C 5H4)2ZrBr2 (C) efficiently. X-ray crystal structures of (eta5-ClMe2Sn-C 5H4)CpZrCl2•1/2toluene, (eta 5-Br2MeSn-C5H4)CpZrBr2•THF, B, and C were obtained. Metallocene C reacts with water to afford an oligosiloxane-supported zirconocene dibromide. Spectroscopic characterization suggested a stereoregular structure in which the metallocene units have meso symmetry. The oligomeric substance showed high activity for homogeneous ethylene polymerization. Supported metallocene olefin polymerization catalysts were prepared by combining a functionalized metallocene precursor (Cp2ZrBr 2 bearing either BrMe2Si or Br2MeSi groups) and partially dehydroxylated silica. The activities of the immobilized zirconocene catalysts decreased and the stabilities increased with increasing number of tethers. The immobilized catalyst prepared from (eta5-Br 2MeSi-C5H4)2ZrBr2, which is assumed to form two "double-tethers" to silica, was significantly more active than the catalyst prepared from [eta5-1,3-(BrMe 2Si)2C5H3]2ZrBr2, which is assumed to form four "single-tethers" to silica. Catalyst leaching was observed in all the immobilized zirconocene catalysts. Finally we report model studies on the stability of the Si-O-Si bonds toward methylaluminoxane (MAO). The reaction of (eta5-BrMe 2Si-C5H4)CpZrBr2 with tBuMe 2SiOH results in the formation of Si-O-Si bonds; addition of NEt 3 results in further reaction to afford Si-O-Zr bonds. The reaction of Me3Si-O-SiMe3 with MAO showed that Si-O-Si bonds can be cleaved under the conditions of our polymerization reactions.

Exposure to welding fumes is associated with hypomethylation of the F2RL3 gene: a cardiovascular disease marker

PubMed Central

Hossain, Mohammad B; Li, Huiqi; Hedmer, Maria; Tinnerberg, Håkan; Albin, Maria; Broberg, Karin

2015-01-01

Background Welders are at risk for cardiovascular disease. Recent studies linked tobacco smoke exposure to hypomethylation of the F2RL3 (coagulation factor II (thrombin) receptor-like 3) gene, a marker for cardiovascular disease prognosis and mortality. However, whether welding fumes cause hypomethylation of F2RL3 remains unknown. Methods We investigated 101 welders (median span of working as a welder: 7 years) and 127 unexposed controls (non-welders with no obvious exposure to respirable dust at work), age range 23–60 years, all currently non-smoking, in Sweden. The participants were interviewed about their work history, lifestyle factors and diseases. Personal sampling of respirable dust was performed for the welders. DNA methylation of F2RL3 in blood was assessed by pyrosequencing of four CpG sites, CpG_2 (corresponds to cg03636183) to CpG_5, in F2RL3. Multivariable linear regression analysis was used to assess the association between exposure to welding fumes and F2RL3 methylation. Results Welders had 2.6% lower methylation of CpG_5 than controls (p<0.001). Higher concentrations of measured respirable dust among the welders were associated with hypomethylation of CpG_2, CpG_4 and CpG_5 (β=−0.49 to −1.4, p<0.012); p<0.029 adjusted for age, previous smoking, passive smoking, education, current residence and respirator use. Increasing the number of years working as a welder was associated with hypomethylation of CpG_4 (linear regression analysis, β=−0.11, p=0.039, adjusted for previous smoking). Previous tobacco smokers had 1.5–4.7% (p<0.014) lower methylation of 3 of the 4 CpG sites in F2RL3 (CpG_2, CpG_4 and CpG_5) compared to never-smokers. A non-significant lower risk of cardiovascular disease with more methylation was observed for all CpG sites. Conclusions Welding fumes exposure and previous smoking were associated with F2RL3 hypomethylation. This finding links low-to-moderate exposure to welding fumes to adverse effects on the cardiovascular system, and suggests a potential mechanistic pathway for this link, via epigenetic effects on F2RL3 expression. PMID:26395445

[Regulatory B cells activated by CpG-ODN combined with anti-CD40 monoclonal antibody inhibit CD4(+)T cell proliferation].

PubMed

Wang, Keng; Tao, Lei; Su, Jianbing; Zhang, Yueyang; Zou, Binhua; Wang, Yiyuan; Li, Xiaojuan

2016-09-01

Objective To observe the immunosuppressive function of regulatory B cells (Bregs) in vitro after activated by CpG oligodeoxynucleotide (CpG-ODN) and anti-CD40 mAb. Methods Mice splenic CD5(+)CD1d(high)B cells and CD5(-)CD1d(low)B cells were sorted by flow cytometry. These B cells were first stimulated with CpG-ODN combined with anti-CD40 mAb for 24 hours, and then co-cultured with purified CD4(+)T cells. The interleukin 10 (IL-10) expression in the activated Bregs and other B cell subset, as well as the proliferation and interferon γ (IFN-γ) expression in the CD4(+) T cells activated by anti-CD3 mAb plus anti-CD28 mAb were determined by flow cytometry. Results CD5(+)CD1d(high) B cells activated by CpG-ODN plus anti-CD40 mAb blocked the up-regulated CD4(+)T proliferation and significantly reduced the IFN-γ level. At the same time, activated CD5(-)CD1d(low)B cells showed no inhibitory effect on CD4(+)T cells. Further study revealed that IL-10 expression in the CD5(+)CD1d(high) B cells were much higher than that in the CD5(-)CD1d(low)B cells after stimulated with CpG-ODN combined with anti-CD40 mAb for 24 hours. Conclusion CD5(+)CD1d(high) B cells activated by CpG-ODN combined with anti-CD40 mAb have immune inhibitory effects on CD4(+)T cell activation in vitro , which possibly due to IL-10 secretion.

50 CFR 679.20 - General limitations.

Code of Federal Regulations, 2010 CFR

2010-10-01

... Type A season B season C season (1) Trawl 60% 20% 20% (i) Trawl CV 70% 10% 20% (ii) Trawl CP 50% 30% 20% (2) Hook-and-line CP and hook-and-line CV ≥60 ft (18.3 m) LOA 60% 40% no C season (3) Jig 40% 20% 40....3 m) LOA 0.2 (4) Hook-and-line CP 48.7 (5) Pot CV ≥60 ft (18.3 m) LOA 8.4 (6) Pot CP 1.5 (7) AFA...

Reaction of BH4- with [Mo2Cp2(mu-SMe)n] species to give tetrahydroborato, hydrido or dimetallaborane compounds: control of product by ancillary ligands.

PubMed

Cabon, Nolwenn; Petillon, Francois Y; Schollhammer, Philippe; Talarmin, Jean; Muir, Kenneth W

2004-09-07

The reaction of mono- or dichloro-dimolybdenum(III) complexes [Mo2Cp2(mu-SMe)2(mu-Cl)(mu-Y)] (Cp=eta5-C5H5; 1, Y=SMe; 2, Y=PPh2; 3, Y=Cl) with NaBH4 at room temperature gave in high yields tetrahydroborato (8), hydrido (9) or metallaborane (12) complexes depending on the ancillary ligands. The correct formulation of derivatives and has been unambigously determined by X-ray diffraction methods. That of the hydrido compound 9 has been established in solution by NMR analysis and confirmed by an X-ray study of the mu-azavinylidene derivative [Mo2Cp2(mu-SMe)2(mu-PPh2)(mu-N=CHMe)] (10) obtained from the insertion of acetonitrile into the Mo-H bond of 9. Reaction of NaBH4 with nitrile derivatives, [Mo2Cp2(mu-SMe)4-n(CH3CN)2n]n+(5, n=1; 6 n=2), afforded the tetrahydroborato compound 8, together with a mu-azavinylidene species [Mo2Cp2(mu-SMe)3(mu-N=CHMe)](14), when n=1, and the metallaborane complex 12, together with a mixed borohydrato-azavinylidene derivative [Mo2Cp2(mu-SMe)2(mu-BH4)(mu-N=CHMe)] (13), when n=2. The molecular structures of these complexes have been confirmed by X-ray analysis. Preparations of some of the starting complexes (3 and 4) are also described, as are the molecular structures of the precursors [Mo2Cp2(mu-SMe)2(mu-X)(mu-Y)] (1, X/Y=Cl/SMe; 2, X/Y=Cl/PPh2; 4, X/Y=SMe/PPh2).

Bradyrhizobium japonicum mutants with enhanced sensitivity to genistein resulting in altered nod gene regulation.

PubMed

Ip, H; D'Aoust, F; Begum, A A; Zhang, H; Smith, D L; Driscoll, B T; Charles, T C

2001-12-01

Bradyrhizobium japonicum mutants with altered nod gene induction characteristics were isolated by screening mutants for genistein-independent nod gene expression. Plasmid pZB32, carrying a nodY::lacZ transcriptional gene fusion, was introduced into B. japonicum cells that had been subjected to UV mutagenesis. Ten independent transformants producing a blue color on plates containing 5bromo-4chloro-3indolyl-beta-D-galactopyranoside but lacking genistein, indicative of constitutive expression of the nodY::lacZ reporter gene, were isolated. Beta-galactosidase activity assays revealed that while all of the 10 strains were sensitive to low concentrations of genistein, none exhibited truly constitutive nodY::lacZ expression in liquid culture. Soybean plants inoculated with three of the mutants were chlorotic and stunted, with shoot dry weights close to those of the uninoculated plants, indicating the absence of nitrogen fixation. Differences in the kinetics of nodY::lacZ expression and lipochitin oligosaccharide Nod signal production suggested that the strains carried different mutations. Some of these strains may be useful in mitigating the low root zone temperature-associated delay in soybean nodulation at the northern extent of soybean cultivation.

NHC carbene supported half-sandwich hydridosilyl complexes of ruthenium: the impact of supporting ligands on Si∙∙∙H interligand interactions.

PubMed

Mai, Van Hung; Kuzmina, Lyudmila G; Churakov, Andrei V; Korobkov, Ilia; Howard, Judith A K; Nikonov, Georgii I

2016-01-07

Reaction of complex [CpRu(pyr)3][PF6] (3) with the NHC carbene IPr (IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene) results in the NHC complex [Cp(IPr)Ru(pyr)2][PF6] (4), which was studied by NMR specroscopy and X-ray diffraction analysis. Reaction of [Cp(IPr)Ru(pyr)2][PF6] (4) with LiAlH4 leads to the trihydride Cp(IPr)RuH3 (5) characterised by spectroscopic methods. Heating compound 5 with hydrosilanes gives the dihydrido silyl derivatives Cp(IPr)RuH2(SiR3) (6). Systematic X-ray diffraction studies suggest that complexes 6 have stronger interligand Si∙∙∙H interactions than the isolobal phosphine complexes Cp(Pr3P)RuH2(SiR3).

Interaction of DRD4 Methylation and Phthalate Metabolites Affects Continuous Performance Test Performance in ADHD.

PubMed

Kim, Johanna Inhyang; Kim, Jae-Won; Shin, Inkyung; Kim, Bung-Nyun

2018-05-01

We investigated the interaction effect between the methylation of dopamine receptor D4 (DRD4) and phthalate exposure in ADHD on continuous performance test (CPT) variables. Urine concentrations of mono-(2-ethyl-5-hydroxyhexyl) phthalate (MEHHP), mono-(2-ethyl-5-oxohexyl) phthalate (MEOHP), and mono-n-butyl phthalate (MBP) were tested. The methylation status was analyzed for CpG sites of DRD4. Multivariable linear regression models were applied to investigate the interaction effects of methylation and phthalate levels. There was a significant interaction effect of the methylation of CpG26 and CpG28 with the MEHHP level on omission errors in ADHD patients, but not in controls. The post hoc analysis revealed a significant correlation between the MEHHP concentration and omission errors in the methylated group, but not in the unmethylated group. The interaction between the methylation status of CpG sites of DRD4, particularly CpG26 and CpG28, and phthalate metabolite levels affects the attention level in ADHD patients.

Synthesis, Structure, Bonding, and Reactivity of Metal Complexes Comprising Diborane(4) and Diborene(2): [{Cp*Mo(CO)2 }2 {μ-η2 :η2 -B2 H4 }] and [{Cp*M(CO)2 }2 B2 H2 M(CO)4 ], M=Mo,W.

PubMed

Mondal, Bijan; Bag, Ranjit; Ghorai, Sagar; Bakthavachalam, K; Jemmis, Eluvathingal D; Ghosh, Sundargopal

2018-07-02

The reaction of [(Cp*Mo) 2 (μ-Cl) 2 B 2 H 6 ] (1) with CO at room temperature led to the formation of the highly fluxional species [{Cp*Mo(CO) 2 } 2 {μ-η 2 :η 2 -B 2 H 4 }] (2). Compound 2, to the best of our knowledge, is the first example of a bimetallic diborane(4) conforming to a singly bridged C s structure. Theoretical studies show that 2 mimics the Cotton dimolybdenum-alkyne complex [{CpMo(CO) 2 } 2 C 2 H 2 ]. In an attempt to replace two hydrogen atoms of diborane(4) in 2 with a 2e [W(CO) 4 ] fragment, [{Cp*Mo(CO) 2 } 2 B 2 H 2 W(CO) 4 ] (3) was isolated upon treatment with [W(CO) 5 ⋅thf]. Compound 3 shows the intriguing presence of [B 2 H 2 ] with a short B-B length of 1.624(4) Å. We isolated the tungsten analogues of 3, [{Cp*W(CO) 2 } 2 B 2 H 2 W(CO) 4 ] (4) and [{Cp*W(CO) 2 } 2 B 2 H 2 Mo(CO) 4 ] (5), which provided direct proof of the existence of the tungsten analogue of 2. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Template-directed synthesis on the pentanucleotide CpCpGpCpC

NASA Technical Reports Server (NTRS)

Inoue, T.; Joyce, G. F.; Grzeskowiak, K.; Orgel, L. E.; Brown, J. M.; Reese, C. B.

1984-01-01

Experiments in which CpCpGpCpC is used as a template to facilitate the co-oligomerization of 2-MeImpG and 2-MeImpC are described. It is shown that 3' to 5' prime-linked pGpGpCpGpG, whose sequence is complementary to that of the template, is substantially the most adundant pentameric product of the template-directed reaction. The yield of pGpGpCpGpG is never large (less than 20 percent), presumably becauase off-template reactions consume template-directed products. Thus pGpGpCpGpG is converted to the various isomers of G5C and G4C2 by off-template terminal addition of G or C. The 3' to 5' isomer of GpG is elongated on the template to give GpGpC, GpGpCpG, and GpGpCpGpG, while the 2' to 5' isomer does not initiate the synthesis of detectable amounts of longer oligomers.

Reduction chemistry of neptunium cyclopentadienide complexes: from structure to understanding† †Electronic supplementary information (ESI) available: General procedures, synthetic details, spectroscopic data, X-ray crystallographic data. CCDC 1524162–1524166. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c7sc00034k Click here for additional data file. Click here for additional data file.

PubMed Central

Dutkiewicz, Michał S.; Apostolidis, Christos

2017-01-01

Neptunium complexes in the formal oxidation states II, III, and IV supported by cyclopentadienyl ligands are explored, and significant differences between Np and U highlighted as a result. A series of neptunium(iii) cyclopentadienyl (Cp) complexes [Np(Cp)3], its bis-acetonitrile adduct [Np(Cp)3(NCMe)2], and its KCp adduct K[Np(Cp)4] and [Np(Cp′)3] (Cp′ = C5H4SiMe3) have been made and characterised providing the first single crystal X-ray analyses of NpIII Cp complexes. In all NpCp3 derivatives there are three Cp rings in η5-coordination around the NpIII centre; additionally in [Np(Cp)3] and K[Np(Cp)4] one Cp ring establishes a μ-η1-interaction to one C atom of a neighbouring Np(Cp)3 unit. The solid state structure of K[Np(Cp)4] is unique in containing two different types of metal–Cp coordination geometries in the same crystal. NpIII(Cp)4 units are found exhibiting four units of η5-coordinated Cp rings like in the known complex [NpIV(Cp)4], the structure of which is now reported. A detailed comparison of the structures gives evidence for the change of ionic radii of ca. –8 pm associated with change in oxidation state between NpIII and NpIV. The rich redox chemistry associated with the syntheses is augmented by the reduction of [Np(Cp′)3] by KC8 in the presence of 2.2.2-cryptand to afford a neptunium(ii) complex that is thermally unstable above –10 °C like the UII and ThII complexes K(2.2.2-cryptand)[Th/U(Cp′)3]. Together, these spontaneous and controlled redox reactions of organo-neptunium complexes, along with information from structural characterisation, show the relevance of organometallic Np chemistry to understanding fundamental structure and bonding in the minor actinides. PMID:28553487

Uranium Hydridoborates: Synthesis, Magnetism, and X-ray/Neutron Diffraction Structures.

PubMed

Braunschweig, H; Gackstatter, A; Kupfer, T; Radacki, K; Franke, S; Meyer, K; Fucke, K; Lemée-Cailleau, M-H

2015-08-17

While uranium hydridoborate complexes containing the [BH4](-) moiety have been well-known in the literature for many years, species with functionalized borate centers remained considerably rare. We were now able to prepare several uranium hydridoborates (1-4) with amino-substituted borate moieties with high selectivity by smooth reaction of [Cp*2UMe2] (Cp* = C5Me5) and [Cp'2UMe2] (Cp' = 1,2,4-tBu3C5H2) with the aminoborane H2BN(SiMe3)2. A combination of nuclear magnetic resonance spectroscopy, deuteration experiments, magnetic SQUID measurements, and X-ray/neutron diffraction studies was used to verify the anticipated molecular structures and oxidation states of 1-4 and helped to establish a linear tridentate coordination mode of the borate anions.

Cannabinoids prevent the acute hyperthermia and partially protect against the 5-HT depleting effects of MDMA ("Ecstasy") in rats.

PubMed

Morley, Kirsten C; Li, Kong M; Hunt, Glenn E; Mallet, Paul E; McGregor, Iain S

2004-06-01

Cannabinoid-MDMA interactions were examined in male Wistar rats. MDMA (4 x 5 mg/kg or 2 x 10 mg/kg over 4 h on each of 2 days) was administered with or without Delta 9-tetrahydrocannabinol (THC) (4 x 2.5 mg/kg), the synthetic cannabinoid receptor agonist CP 55,940 (2 x 0.1 or 0.2 mg/kg) or the cannabinoid receptor antagonist SR 141716 (2 x 5 mg/kg). Co-administered Delta 9-THC and CP 55,940 but not SR 141716 prevented MDMA-induced hyperthermia, causing a powerful hypothermia. Co-administered Delta 9-THC, CP 55,940 and SR 141716 all tended to decrease MDMA-induced hyperactivity. Co-administered Delta 9-THC provided protection against the long-term increases in anxiety seen in the emergence test, but not the social interaction test, 6 weeks after MDMA treatment. Co-administered Delta 9-THC and CP 55,940, but not SR 141716, partly prevented the long-term 5-HT and 5-HIAA depletion caused by MDMA in various brain regions. SR 141716 administered with CP 55,940 and MDMA prevented the hypothermic response to the CP 55,940/MDMA combination but did not alter the CP 55,940 attenuation of MDMA-induced 5-HT depletion. These results suggest a partial protective effect of co-administered cannabinoid receptor agonists on MDMA-induced 5-HT depletion and long-term anxiety. This action appears to operate independently of cannabinoid CB1 receptors.

cyclo-P4 Building Blocks: Achieving Non-Classical Fullerene Topology and Beyond.

PubMed

Dielmann, Fabian; Peresypkina, Eugenia V; Krämer, Barbara; Hastreiter, Florian; Johnson, Brian P; Zabel, Manfred; Heindl, Claudia; Scheer, Manfred

2016-11-14

The cyclo-P 4 complexes [Cp R Ta(CO) 2 (η 4 -P 4 )] (Cp R : Cp''=1,3-C 5 H 3 tBu 2 , Cp'''=1,2,4-C 5 H 2 tBu 3 ) turned out to be predestined for the formation of hollow spherical supramolecules with non-classical fullerene-like topology. The resulting assemblies constructed with CuX (X=Cl, Br) showed a highly symmetric 32-vertex core of solely four- and six-membered rings. In some supramolecules, the inner cavity was occupied by an additional CuX unit. On the other hand, using CuI, two different supramolecules with either peanut- or pear-like shapes and outer diameters in the range of 2-2.5 nm were isolated. Furthermore, the spherical supramolecules containing Cp''' ligands at tantalum are soluble in CH 2 Cl 2 . NMR spectroscopic investigations in solution revealed the formation of isomeric supramolecules owing to the steric hindrance caused by the third tBu group on the Cp''' ligand. In addition, a 2D coordination polymer was obtained and structurally characterized. © 2016 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

η(4) -HBCC-σ,π-Borataallyl Complexes of Ruthenium Comprising an Agostic Interaction.

PubMed

Saha, Koushik; Joseph, Benson; Ramalakshmi, Rongala; Anju, R S; Varghese, Babu; Ghosh, Sundargopal

2016-06-01

Thermolysis of [Cp*Ru(PPh2 (CH2 )PPh2 )BH2 (L2 )] 1 (Cp*=η(5) -C5 Me5 ; L=C7 H4 NS2 ), with terminal alkynes led to the formation of η(4) -σ,π-borataallyl complexes [Cp*Ru(μ-H)B{R-C=CH2 }(L)2 ] (2 a-c) and η(2) -vinylborane complexes [Cp*Ru(R-C=CH2 )BH(L)2 ] (3 a-c) (2 a, 3 a: R=Ph; 2 b, 3 b: R=COOCH3 ; 2 c, 3 c: R=p-CH3 -C6 H4 ; L=C7 H4 NS2 ) through hydroboration reaction. Ruthenium and the HBCC unit of the vinylborane moiety in 2 a-c are linked by a unique η(4) -interaction. Conversions of 1 into 3 a-c proceed through the formation of intermediates 2 a-c. Furthermore, in an attempt to expand the library of these novel complexes, chemistry of σ-borane complex [Cp*RuCO(μ-H)BH2 L] 4 (L=C7 H4 NS2 ) was investigated with both internal and terminal alkynes. Interestingly, under photolytic conditions, 4 reacts with methyl propiolate to generate the η(4) -σ,π-borataallyl complexes [Cp*Ru(μ-H)BH{R-C=CH2 }(L)] 5 and [Cp*Ru(μ-H)BH{HC=CH-R}(L)] 6 (R=COOCH3 ; L=C7 H4 NS2 ) by Markovnikov and anti-Markovnikov hydroboration. In an extension, photolysis of 4 in the presence of dimethyl acetylenedicarboxylate yielded η(4) -σ,π-borataallyl complex [Cp*Ru(μ-H)BH{R-C=CH-R}(L)] 7 (R=COOCH3 ; L=C7 H4 NS2 ). An agostic interaction was also found to be present in 2 a-c and 5-7, which is rare among the borataallyl complexes. All the new compounds have been characterized in solution by IR, (1) H, (11) B, (13) C NMR spectroscopy, mass spectrometry and the structural types were unequivocally established by crystallographic analysis of 2 b, 3 a-c and 5-7. DFT calculations were performed to evaluate possible bonding and electronic structures of the new compounds. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Coordination Polymers Derived from Non-Steroidal Anti-Inflammatory Drugs for Cell Imaging and Drug Delivery.

PubMed

Paul, Mithun; Dastidar, Parthasarathi

2016-01-18

A new series of Mn(II) coordination polymers, namely, [{Mn(L)(H2 O)2 }⋅2 Nap]∞ (CP1), [{Mn(L)(Ibu)2 (H2 O)2 }]∞ (CP2), [{Mn(L)(Flr)2 (H2 O)2 }]∞ (CP3), [{Mn(L)(Ind)2 (H2 O)2 }⋅H2 O]∞ (CP4), [{Mn2 (L)2 (μ-Flu)4 (H2 O)}⋅L]∞ (CP5), [{Mn2 (L)2 (μ-Tol)4 (H2 O)2 }]∞ (CP6) and [{Mn2 (L)2 (μ-Mef)4 (H2 O)2 }]∞ (CP7) (Nap=naproxen, Ibu=ibuprofen, Flr=flurbiprofen, Ind=indometacin, Flu=flufenamic acid, Tol=tolfenamic acid and Mef=mefenamic acid) derived from various non-steroidal anti-inflammatory drugs (NSAIDs) and the organic linker 1,2-bis(4-pyridyl)ethylene (L) have been synthesized with the aim of being used for cell imaging and drug delivery. Single-crystal X-ray diffraction (SXRD) studies revealed that the NSAID molecules were part of the coordination polymeric network either through coordination to the metal center (in the majority of the cases) or through hydrogen bonding. Remarkably, all the Mn(II) coordination polymers were found to be soluble in DMSO, thereby making them particularly suitable for the desired biological applications. Two of the coordination polymers (namely, CP1 and CP3) reported herein, were found to be photoluminescent both in the solid as well as in the solution state. Subsequent experiments (namely, MTT (3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide), and PGE2 (prostaglandin E2 ) assays) established their biocompatibility and anti-inflammatory response. In vitro studies by using a macrophage cell line (i.e., RAW 264.7) revealed that both CP1 and CP3 were excellent cell imaging agents. Finally, biodegradability studies under simulated physiological conditions in phosphate-buffered saline (PBS) at pH 7.6 showed that slow and sustained release of the corresponding NSAID was indeed possible from both CP1 and CP3. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Exposure to welding fumes is associated with hypomethylation of the F2RL3 gene: a cardiovascular disease marker.

PubMed

Hossain, Mohammad B; Li, Huiqi; Hedmer, Maria; Tinnerberg, Håkan; Albin, Maria; Broberg, Karin

2015-12-01

Welders are at risk for cardiovascular disease. Recent studies linked tobacco smoke exposure to hypomethylation of the F2RL3 (coagulation factor II (thrombin) receptor-like 3) gene, a marker for cardiovascular disease prognosis and mortality. However, whether welding fumes cause hypomethylation of F2RL3 remains unknown. We investigated 101 welders (median span of working as a welder: 7 years) and 127 unexposed controls (non-welders with no obvious exposure to respirable dust at work), age range 23-60 years, all currently non-smoking, in Sweden. The participants were interviewed about their work history, lifestyle factors and diseases. Personal sampling of respirable dust was performed for the welders. DNA methylation of F2RL3 in blood was assessed by pyrosequencing of four CpG sites, CpG_2 (corresponds to cg03636183) to CpG_5, in F2RL3. Multivariable linear regression analysis was used to assess the association between exposure to welding fumes and F2RL3 methylation. Welders had 2.6% lower methylation of CpG_5 than controls (p<0.001). Higher concentrations of measured respirable dust among the welders were associated with hypomethylation of CpG_2, CpG_4 and CpG_5 (β=-0.49 to -1.4, p<0.012); p<0.029 adjusted for age, previous smoking, passive smoking, education, current residence and respirator use. Increasing the number of years working as a welder was associated with hypomethylation of CpG_4 (linear regression analysis, β=-0.11, p=0.039, adjusted for previous smoking). Previous tobacco smokers had 1.5-4.7% (p<0.014) lower methylation of 3 of the 4 CpG sites in F2RL3 (CpG_2, CpG_4 and CpG_5) compared to never-smokers. A non-significant lower risk of cardiovascular disease with more methylation was observed for all CpG sites. Welding fumes exposure and previous smoking were associated with F2RL3 hypomethylation. This finding links low-to-moderate exposure to welding fumes to adverse effects on the cardiovascular system, and suggests a potential mechanistic pathway for this link, via epigenetic effects on F2RL3 expression. Published by the BMJ Publishing Group Limited. For permission to use (where not already granted under a licence) please go to http://www.bmj.com/company/products-services/rights-and-licensing/

The roles of 4f- and 5f-orbitals in bonding: a magnetochemical, crystal field, density functional theory, and multi-reference wavefunction study

DOE PAGES

Lukens, W. W.; Speldrich, M.; Yang, P.; ...

2016-01-01

The electronic structures of 4f 3/5f 3Cp" 3M and Cp"sub>3M·alkylisocyanide complexes, where Cp" is 1,3-bis-(trimethylsilyl)cyclopentadienyl, are explored with a focus on the splitting of the f-orbitals, which provides information about the strengths of the metal–ligand interactions.

Measurement of the CP asymmetry in B - → D s - D 0 and B - → D - D 0 decays

NASA Astrophysics Data System (ADS)

Aaij, R.; Adeva, B.; Adinolfi, M.; Ajaltouni, Z.; Akar, S.; Albicocco, P.; Albrecht, J.; Alessio, F.; Alexander, M.; Alfonso Albero, A.; Ali, S.; Alkhazov, G.; Alvarez Cartelle, P.; Alves, A. A.; Amato, S.; Amerio, S.; Amhis, Y.; An, L.; Anderlini, L.; Andreassi, G.; Andreotti, M.; Andrews, J. E.; Appleby, R. B.; Archilli, F.; d'Argent, P.; Arnau Romeu, J.; Artamonov, A.; Artuso, M.; Aslanides, E.; Atzeni, M.; Auriemma, G.; Bachmann, S.; Back, J. J.; Baker, S.; Balagura, V.; Baldini, W.; Baranov, A.; Barlow, R. J.; Barsuk, S.; Barter, W.; Baryshnikov, F.; Batozskaya, V.; Battista, V.; Bay, A.; Beddow, J.; Bedeschi, F.; Bediaga, I.; Beiter, A.; Bel, L. J.; Beliy, N.; Bellee, V.; Belloli, N.; Belous, K.; Belyaev, I.; Ben-Haim, E.; Bencivenni, G.; Benson, S.; Beranek, S.; Berezhnoy, A.; Bernet, R.; Berninghoff, D.; Bertholet, E.; Bertolin, A.; Betancourt, C.; Betti, F.; Bettler, M. O.; van Beuzekom, M.; Bezshyiko, Ia.; Bifani, S.; Billoir, P.; Birnkraut, A.; Bizzeti, A.; Bjørn, M.; Blake, T.; Blanc, F.; Blusk, S.; Bocci, V.; Boente Garcia, O.; Boettcher, T.; Bondar, A.; Bondar, N.; Borghi, S.; Borisyak, M.; Borsato, M.; Bossu, F.; Boubdir, M.; Bowcock, T. J. V.; Bowen, E.; Bozzi, C.; Braun, S.; Brodski, M.; Brodzicka, J.; Brundu, D.; Buchanan, E.; Burr, C.; Bursche, A.; Buytaert, J.; Byczynski, W.; Cadeddu, S.; Cai, H.; Calabrese, R.; Calladine, R.; Calvi, M.; Calvo Gomez, M.; Camboni, A.; Campana, P.; Campora Perez, D. H.; Capriotti, L.; Carbone, A.; Carboni, G.; Cardinale, R.; Cardini, A.; Carniti, P.; Carson, L.; Carvalho Akiba, K.; Casse, G.; Cassina, L.; Cattaneo, M.; Cavallero, G.; Cenci, R.; Chamont, D.; Chapman, M. G.; Charles, M.; Charpentier, Ph.; Chatzikonstantinidis, G.; Chefdeville, M.; Chen, S.; Chitic, S.-G.; Chobanova, V.; Chrzaszcz, M.; Chubykin, A.; Ciambrone, P.; Cid Vidal, X.; Ciezarek, G.; Clarke, P. E. L.; Clemencic, M.; Cliff, H. V.; Closier, J.; Coco, V.; Cogan, J.; Cogneras, E.; Cogoni, V.; Cojocariu, L.; Collins, P.; Colombo, T.; Comerma-Montells, A.; Contu, A.; Coombs, G.; Coquereau, S.; Corti, G.; Corvo, M.; Costa Sobral, C. M.; Couturier, B.; Cowan, G. A.; Craik, D. C.; Crocombe, A.; Cruz Torres, M.; Currie, R.; D'Ambrosio, C.; Da Cunha Marinho, F.; Da Silva, C. L.; Dall'Occo, E.; Dalseno, J.; Danilina, A.; Davis, A.; De Aguiar Francisco, O.; De Bruyn, K.; De Capua, S.; De Cian, M.; De Miranda, J. M.; De Paula, L.; De Serio, M.; De Simone, P.; Dean, C. T.; Decamp, D.; Del Buono, L.; Delaney, B.; Dembinski, H.-P.; Demmer, M.; Dendek, A.; Derkach, D.; Deschamps, O.; Dettori, F.; Dey, B.; Di Canto, A.; Di Nezza, P.; Didenko, S.; Dijkstra, H.; Dordei, F.; Dorigo, M.; Dosil Suárez, A.; Douglas, L.; Dovbnya, A.; Dreimanis, K.; Dufour, L.; Dujany, G.; Durante, P.; Durham, J. M.; Dutta, D.; Dzhelyadin, R.; Dziewiecki, M.; Dziurda, A.; Dzyuba, A.; Easo, S.; Egede, U.; Egorychev, V.; Eidelman, S.; Eisenhardt, S.; Eitschberger, U.; Ekelhof, R.; Eklund, L.; Ely, S.; Ene, A.; Escher, S.; Esen, S.; Evans, H. M.; Evans, T.; Falabella, A.; Farley, N.; Farry, S.; Fazzini, D.; Federici, L.; Fernandez, G.; Fernandez Declara, P.; Fernandez Prieto, A.; Ferrari, F.; Ferreira Lopes, L.; Ferreira Rodrigues, F.; Ferro-Luzzi, M.; Filippov, S.; Fini, R. A.; Fiorini, M.; Firlej, M.; Fitzpatrick, C.; Fiutowski, T.; Fleuret, F.; Fontana, M.; Fontanelli, F.; Forty, R.; Franco Lima, V.; Frank, M.; Frei, C.; Fu, J.; Funk, W.; Färber, C.; Gabriel, E.; Gallas Torreira, A.; Galli, D.; Gallorini, S.; Gambetta, S.; Gandelman, M.; Gandini, P.; Gao, Y.; Garcia Martin, L. M.; Garcia Plana, B.; García Pardiñas, J.; Garra Tico, J.; Garrido, L.; Gascon, D.; Gaspar, C.; Gavardi, L.; Gazzoni, G.; Gerick, D.; Gersabeck, E.; Gersabeck, M.; Gershon, T.; Ghez, Ph.; Gianí, S.; Gibson, V.; Girard, O. G.; Giubega, L.; Gizdov, K.; Gligorov, V. V.; Golubkov, D.; Golutvin, A.; Gomes, A.; Gorelov, I. V.; Gotti, C.; Govorkova, E.; Grabowski, J. P.; Graciani Diaz, R.; Granado Cardoso, L. A.; Graugés, E.; Graverini, E.; Graziani, G.; Grecu, A.; Greim, R.; Griffith, P.; Grillo, L.; Gruber, L.; Gruberg Cazon, B. R.; Grünberg, O.; Gushchin, E.; Guz, Yu.; Gys, T.; Göbel, C.; Hadavizadeh, T.; Hadjivasiliou, C.; Haefeli, G.; Haen, C.; Haines, S. C.; Hamilton, B.; Han, X.; Hancock, T. H.; Hansmann-Menzemer, S.; Harnew, N.; Harnew, S. T.; Hasse, C.; Hatch, M.; He, J.; Hecker, M.; Heinicke, K.; Heister, A.; Hennessy, K.; Henry, L.; van Herwijnen, E.; Heß, M.; Hicheur, A.; Hill, D.; Hopchev, P. H.; Hu, W.; Huang, W.; Huard, Z. C.; Hulsbergen, W.; Humair, T.; Hushchyn, M.; Hutchcroft, D.; Ibis, P.; Idzik, M.; Ilten, P.; Ivshin, K.; Jacobsson, R.; Jalocha, J.; Jans, E.; Jawahery, A.; Jiang, F.; John, M.; Johnson, D.; Jones, C. R.; Joram, C.; Jost, B.; Jurik, N.; Kandybei, S.; Karacson, M.; Kariuki, J. M.; Karodia, S.; Kazeev, N.; Kecke, M.; Keizer, F.; Kelsey, M.; Kenzie, M.; Ketel, T.; Khairullin, E.; Khanji, B.; Khurewathanakul, C.; Kim, K. E.; Kirn, T.; Klaver, S.; Klimaszewski, K.; Klimkovich, T.; Koliiev, S.; Kolpin, M.; Kopecna, R.; Koppenburg, P.; Kotriakhova, S.; Kozeiha, M.; Kravchuk, L.; Kreps, M.; Kress, F.; Krokovny, P.; Krupa, W.; Krzemien, W.; Kucewicz, W.; Kucharczyk, M.; Kudryavtsev, V.; Kuonen, A. K.; Kvaratskheliya, T.; Lacarrere, D.; Lafferty, G.; Lai, A.; Lanfranchi, G.; Langenbruch, C.; Latham, T.; Lazzeroni, C.; Le Gac, R.; Leflat, A.; Lefrançois, J.; Lefèvre, R.; Lemaitre, F.; Lenisa, P.; Leroy, O.; Lesiak, T.; Leverington, B.; Li, P.-R.; Li, T.; Li, Z.; Liang, X.; Likhomanenko, T.; Lindner, R.; Lionetto, F.; Lisovskyi, V.; Liu, X.; Loh, D.; Loi, A.; Longstaff, I.; Lopes, J. H.; Lucchesi, D.; Lucio Martinez, M.; Lupato, A.; Luppi, E.; Lupton, O.; Lusiani, A.; Lyu, X.; Machefert, F.; Maciuc, F.; Macko, V.; Mackowiak, P.; Maddrell-Mander, S.; Maev, O.; Maguire, K.; Maisuzenko, D.; Majewski, M. W.; Malde, S.; Malecki, B.; Malinin, A.; Maltsev, T.; Manca, G.; Mancinelli, G.; Marangotto, D.; Maratas, J.; Marchand, J. F.; Marconi, U.; Marin Benito, C.; Marinangeli, M.; Marino, P.; Marks, J.; Martellotti, G.; Martin, M.; Martinelli, M.; Martinez Santos, D.; Martinez Vidal, F.; Massafferri, A.; Matev, R.; Mathad, A.; Mathe, Z.; Matteuzzi, C.; Mauri, A.; Maurice, E.; Maurin, B.; Mazurov, A.; McCann, M.; McNab, A.; McNulty, R.; Mead, J. V.; Meadows, B.; Meaux, C.; Meier, F.; Meinert, N.; Melnychuk, D.; Merk, M.; Merli, A.; Michielin, E.; Milanes, D. A.; Millard, E.; Minard, M.-N.; Minzoni, L.; Mitzel, D. S.; Mogini, A.; Molina Rodriguez, J.; Mombächer, T.; Monroy, I. A.; Monteil, S.; Morandin, M.; Morello, G.; Morello, M. J.; Morgunova, O.; Moron, J.; Morris, A. B.; Mountain, R.; Muheim, F.; Mulder, M.; Müller, D.; Müller, J.; Müller, K.; Müller, V.; Naik, P.; Nakada, T.; Nandakumar, R.; Nandi, A.; Nasteva, I.; Needham, M.; Neri, N.; Neubert, S.; Neufeld, N.; Neuner, M.; Nguyen, T. D.; Nguyen-Mau, C.; Nieswand, S.; Niet, R.; Nikitin, N.; Nogay, A.; O'Hanlon, D. P.; Oblakowska-Mucha, A.; Obraztsov, V.; Ogilvy, S.; Oldeman, R.; Onderwater, C. J. G.; Ossowska, A.; Otalora Goicochea, J. M.; Owen, P.; Oyanguren, A.; Pais, P. R.; Palano, A.; Palutan, M.; Panshin, G.; Papanestis, A.; Pappagallo, M.; Pappalardo, L. L.; Parker, W.; Parkes, C.; Passaleva, G.; Pastore, A.; Patel, M.; Patrignani, C.; Pearce, A.; Pellegrino, A.; Penso, G.; Pepe Altarelli, M.; Perazzini, S.; Pereima, D.; Perret, P.; Pescatore, L.; Petridis, K.; Petrolini, A.; Petrov, A.; Petruzzo, M.; Pietrzyk, B.; Pietrzyk, G.; Pikies, M.; Pinci, D.; Pisani, F.; Pistone, A.; Piucci, A.; Placinta, V.; Playfer, S.; Plo Casasus, M.; Polci, F.; Poli Lener, M.; Poluektov, A.; Polukhina, N.; Polyakov, I.; Polycarpo, E.; Pomery, G. J.; Ponce, S.; Popov, A.; Popov, D.; Poslavskii, S.; Potterat, C.; Price, E.; Prisciandaro, J.; Prouve, C.; Pugatch, V.; Puig Navarro, A.; Pullen, H.; Punzi, G.; Qian, W.; Qin, J.; Quagliani, R.; Quintana, B.; Rachwal, B.; Rademacker, J. H.; Rama, M.; Ramos Pernas, M.; Rangel, M. S.; Ratnikov, F.; Raven, G.; Ravonel Salzgeber, M.; Reboud, M.; Redi, F.; Reichert, S.; dos Reis, A. C.; Remon Alepuz, C.; Renaudin, V.; Ricciardi, S.; Richards, S.; Rinnert, K.; Robbe, P.; Robert, A.; Rodrigues, A. B.; Rodrigues, E.; Rodriguez Lopez, J. A.; Rogozhnikov, A.; Roiser, S.; Rollings, A.; Romanovskiy, V.; Romero Vidal, A.; Rotondo, M.; Rudolph, M. S.; Ruf, T.; Ruiz Vidal, J.; Saborido Silva, J. J.; Sagidova, N.; Saitta, B.; Salustino Guimaraes, V.; Sanchez Mayordomo, C.; Sanmartin Sedes, B.; Santacesaria, R.; Santamarina Rios, C.; Santimaria, M.; Santovetti, E.; Sarpis, G.; Sarti, A.; Satriano, C.; Satta, A.; Savrina, D.; Schael, S.; Schellenberg, M.; Schiller, M.; Schindler, H.; Schmelling, M.; Schmelzer, T.; Schmidt, B.; Schneider, O.; Schopper, A.; Schreiner, H. F.; Schubiger, M.; Schune, M. H.; Schwemmer, R.; Sciascia, B.; Sciubba, A.; Semennikov, A.; Sepulveda, E. S.; Sergi, A.; Serra, N.; Serrano, J.; Sestini, L.; Seyfert, P.; Shapkin, M.; Shcheglov, Y.; Shears, T.; Shekhtman, L.; Shevchenko, V.; Siddi, B. G.; Silva Coutinho, R.; Silva de Oliveira, L.; Simi, G.; Simone, S.; Skidmore, N.; Skwarnicki, T.; Smith, I. T.; Smith, M.; Soares Lavra, l.; Sokoloff, M. D.; Soler, F. J. P.; Souza De Paula, B.; Spaan, B.; Spradlin, P.; Stagni, F.; Stahl, M.; Stahl, S.; Stefko, P.; Stefkova, S.; Steinkamp, O.; Stemmle, S.; Stenyakin, O.; Stepanova, M.; Stevens, H.; Stone, S.; Storaci, B.; Stracka, S.; Stramaglia, M. E.; Straticiuc, M.; Straumann, U.; Strokov, S.; Sun, J.; Sun, L.; Swientek, K.; Syropoulos, V.; Szumlak, T.; Szymanski, M.; T'Jampens, S.; Tang, Z.; Tayduganov, A.; Tekampe, T.; Tellarini, G.; Teubert, F.; Thomas, E.; van Tilburg, J.; Tilley, M. J.; Tisserand, V.; Tobin, M.; Tolk, S.; Tomassetti, L.; Tonelli, D.; Tourinho Jadallah Aoude, R.; Tournefier, E.; Traill, M.; Tran, M. T.; Tresch, M.; Trisovic, A.; Tsaregorodtsev, A.; Tully, A.; Tuning, N.; Ukleja, A.; Usachov, A.; Ustyuzhanin, A.; Uwer, U.; Vacca, C.; Vagner, A.; Vagnoni, V.; Valassi, A.; Valat, S.; Valenti, G.; Vazquez Gomez, R.; Vazquez Regueiro, P.; Vecchi, S.; van Veghel, M.; Velthuis, J. J.; Veltri, M.; Veneziano, G.; Venkateswaran, A.; Verlage, T. A.; Vernet, M.; Vesterinen, M.; Viana Barbosa, J. V.; Vieira, D.; Vieites Diaz, M.; Viemann, H.; Vilasis-Cardona, X.; Vitkovskiy, A.; Vitti, M.; Volkov, V.; Vollhardt, A.; Voneki, B.; Vorobyev, A.; Vorobyev, V.; Voß, C.; de Vries, J. A.; Vázquez Sierra, C.; Waldi, R.; Walsh, J.; Wang, J.; Wang, M.; Wang, Y.; Wang, Z.; Ward, D. R.; Wark, H. M.; Watson, N. K.; Websdale, D.; Weiden, A.; Weisser, C.; Whitehead, M.; Wicht, J.; Wilkinson, G.; Wilkinson, M.; Williams, M. R. J.; Williams, M.; Williams, T.; Wilson, F. F.; Wimberley, J.; Winn, M.; Wishahi, J.; Wislicki, W.; Witek, M.; Wormser, G.; Wotton, S. A.; Wyllie, K.; Xiao, D.; Xie, Y.; Xu, A.; Xu, M.; Xu, Q.; Xu, Z.; Xu, Z.; Yang, Z.; Yang, Z.; Yao, Y.; Yin, H.; Yu, J.; Yuan, X.; Yushchenko, O.; Zarebski, K. A.; Zavertyaev, M.; Zhang, L.; Zhang, Y.; Zhelezov, A.; Zheng, Y.; Zhu, X.; Zhukov, V.; Zonneveld, J. B.; Zucchelli, S.

2018-05-01

The CP asymmetry in B - → D s - D 0 and B - → D - D 0 decays is measured using LHCb data corresponding to an integrated luminosity of 3.0 fb-1, collected in pp collisions at centre-of-mass energies of 7 and 8 TeV. The results are A^{CP}({B}-\\to {D}_s-{D}^0)=(-0.4± 0.5± 0.5) and A^{CP}({B}-\\to {D}-{D}^0)=(2.3± 2.7± 0.4)% , where the first uncertainties are statistical and the second systematic. This is the first measurement of A^{CP}({B}-\\to {D}_s-{D}^0) and the most precise determination of A^{CP}({B}-\\to {D}-{D}^0) . Neither result shows evidence of CP violation. [Figure not available: see fulltext.

Two Alternative Pathways for the Synthesis of the Rare Compatible Solute Mannosylglucosylglycerate in Petrotoga mobilis▿

PubMed Central

Fernandes, Chantal; Mendes, Vitor; Costa, Joana; Empadinhas, Nuno; Jorge, Carla; Lamosa, Pedro; Santos, Helena; da Costa, Milton S.

2010-01-01

The compatible solute mannosylglucosylglycerate (MGG), recently identified in Petrotoga miotherma, also accumulates in Petrotoga mobilis in response to hyperosmotic conditions and supraoptimal growth temperatures. Two functionally connected genes encoding a glucosyl-3-phosphoglycerate synthase (GpgS) and an unknown glycosyltransferase (gene Pmob_1143), which we functionally characterized as a mannosylglucosyl-3-phosphoglycerate synthase and designated MggA, were identified in the genome of Ptg. mobilis. This enzyme used the product of GpgS, glucosyl-3-phosphoglycerate (GPG), as well as GDP-mannose to produce mannosylglucosyl-3-phosphoglycerate (MGPG), the phosphorylated precursor of MGG. The MGPG dephosphorylation was determined in cell extracts, and the native enzyme was partially purified and characterized. Surprisingly, a gene encoding a putative glucosylglycerate synthase (Ggs) was also identified in the genome of Ptg. mobilis, and an active Ggs capable of producing glucosylglycerate (GG) from ADP-glucose and d-glycerate was detected in cell extracts and the recombinant enzyme was characterized, as well. Since GG has never been identified in this organism nor was it a substrate for the MggA, we anticipated the existence of a nonphosphorylating pathway for MGG synthesis. We putatively identified the corresponding gene, whose product had some sequence homology with MggA, but it was not possible to recombinantly express a functional enzyme from Ptg. mobilis, which we named mannosylglucosylglycerate synthase (MggS). In turn, a homologous gene from Thermotoga maritima was successfully expressed, and the synthesis of MGG was confirmed from GDP-mannose and GG. Based on the measurements of the relevant enzyme activities in cell extracts and on the functional characterization of the key enzymes, we propose two alternative pathways for the synthesis of the rare compatible solute MGG in Ptg. mobilis. PMID:20061481

Zirconocene-iridium hydrido complexes: arene carbon-hydrogen bond activation and formation of a planar square Zr2Ir2 complex.

PubMed

Oishi, Masataka; Suzuki, Hiroharu

2009-03-16

New early-late heterobimetallic hydrides (L(2)ZrCl)(Cp*Ir)(mu-H)(3) (1; L = Cp derivative, Cp* = eta(5)-C(5)Me(5)) were synthesized from zirconocene derivatives (L(2)ZrCl(2)) and LiCp*IrH(3) via a salt elimination reaction and structurally characterized by NMR and X-ray analyses. Upon treatment of 1 with an alkyllithium reagent, hydride abstraction complex 4 underwent thermolytic ligand elimination at the Zr-Ir system to yield a novel planar square complex (L(2)Zr)(2)(Cp*Ir)(2)(mu(3)-H)(4) (2). When a labeling study of the reaction was conducted, it was found that the conversion of 1 to 2 involves rapid aromatic and benzylic C-H activation by a coordinatively unsaturated dinuclear complex (L(2)Zr)(Cp*Ir)(H)(2) (3).

Mechanistic investigations of CO-photoextrusion and oxidative addition reactions of early transition-metal carbonyls: (η(5)-C5H5)M(CO)4 (M = V, Nb, Ta).

PubMed

Su, Shih-Hao; Su, Ming-Der

2016-06-28

The mechanisms for the photochemical Si-H bond activation reaction are studied theoretically using a model system of the group 5 organometallic compounds, η(5)-CpM(CO)4 (M = V, Nb, and Ta), with the M06-2X method and the Def2-SVPD basis set. Three types of reaction pathways that lead to final insertion products are identified. The structures of the intersystem crossings, which play a central role in these photo-activation reactions, are determined. The intermediates and transitional structures in either the singlet or triplet states are also calculated to provide a mechanistic explanation of the reaction pathways. All of the potential energy surfaces for the group 5 η(5)-CpM(CO)4 complexes are quite similar. In particular, the theoretical evidence suggests that after irradiation using light, η(5)-CpM(CO)4 quickly loses one CO ligand to yield two tricarbonyls, in either the singlet or the triplet states. The triplet tricarbonyl 16-electron intermediates, ([η(5)-CpM(CO)3](3)), play a key role in the formation of the final oxidative addition product, η(5)-CpM(CO)3(H)(SiMe3). However, the singlet counterparts, ([η(5)-CpM(CO)3](1)), play no role in the formation of the final product molecule, but their singlet metal centers interact weakly with solvent molecules ((Me3)SiH) to produce alkyl-solvated organometallic complexes, which are observable experimentally. This theoretical evidence is in accordance with the available experimental observations.

Vehicle Mobility Assessment for Project Wheels Study Group

DTIC Science & Technology

1972-07-01

cash savings p’Asible through the elimination of special military automotive features, such as front-wheel 1 Idrive , or the use of commercial vehicles...E12. (12) off-,,,d mobiliY profile 4x4 0ruck, c 2Z4< 20 ,ernn It Iot "- III IIIII III I I I IIII A%. West Germany 0A * s ps ArizonazD • Ř’.. • D

Electronic Structure and Multisite Basicity of the Pyramidal Phosphinidene-Bridged Dimolybdenum Complex [Mo2(η(5)-C5H5)(μ-κ(1):κ(1),η(5)-PC5H4)(η(6)-C6H3(t)Bu3)(CO)2(PMe3)].

PubMed

Albuerne, Isabel G; Alvarez, M Angeles; García, M Esther; García-Vivó, Daniel; Ruiz, Miguel A

2015-10-19

The title phosphinidene complex could be sequentially protonated with HBF4·OEt2 or [H(OEt2)2](BAr'4) to give the phosphido-bridged derivatives [Mo2Cp(μ-κ(1):κ(1),η(5)-HPC5H4)(η(6)-HMes*)(CO)2(PMe3)]X and then the hydrides [Mo2Cp(H)(μ-κ(1):κ(1),η(5)-HPC5H4)(η(6)-HMes*)(CO)2(PMe3)]X2 (X = BF4, BAr'4; Ar' = 3,5-C6H3(CF3)2; Mes* = 2,4,6-C6H2(t)Bu3). Density functional theory (DFT) calculations revealed that the most favored site for initial electrophilic attack is the metallocene Mo atom, but attachment of the electrophile to the phosphinidene P atom gives more stable products. This was in agreement with all other reactions investigated, which invariably involved the attachment of the added electrophile at the P site. Thus, the title compound reacted with S8 at 223 K to give the thiophosphinidene-bridged complex [Mo2Cp{μ-κ(1):κ(1),η(5)-P(S)C5H4}(η(6)-HMes*)(CO)2(PMe3)], a poorly stable molecule which reacted with MeI at room temperature to give the corresponding thiolatophosphido derivative, isolated as [Mo2Cp{μ-κ(1):κ(1),η(5)-P(SMe)C5H4}(η(6)-HMes*)(CO)2(PMe3)](BAr'4) (P-S = 2.128(4) Å) after anion exchange with Na(BAr'4). Reaction of the title compound with MeI proceeded smoothly to give the corresponding methylphosphido derivative, isolated analogously as [Mo2Cp{μ-κ(1):κ(1),η(5)-P(Me)C5H4}(η(6)-HMes*)(CO)2(PMe3)](BAr'4). The related complex [Mo2Cp{μ-κ(1):κ(1),η(5)-P(Me)C5H4}(η(6)-HMes*)(CO)2(PMe2Ph)](BAr'4) (P-C(Me) = 1.841(5) Å) could be prepared analogously from the neutral precursor [Mo2Cp{μ-κ(1):κ(1),η(5)-PC5H4}(η(6)-HMes*)(CO)2(PMe2Ph)]. In contrast, reaction of the title complex with ethylene sulfide involved opening of the C2S ring and formation of new P-C and Mo-S bonds (1.886(7) and 2.493(2) Å, respectively), with displacement of the PMe3 ligand, to give the phosphido-thiolato complex [Mo2Cp{μ-κ(2)(P,S):κ(1)P,η(5)-P(C2H4S)C5H4}(η(6)-HMes*)(CO)2]. All these derivatives of the title complex displayed an unusual trigonal pyramidal-like environment around the bridging P atom, with the added electrophile placed in the Mo2P plane as a result of the directionality of the relevant frontier orbital of the phosphinidene complex, according to DFT calculations.

Synthesis of Ruthenium Carbonyl Complexes with Phosphine or Substituted Cp Ligands, and Their Activity in the Catalytic Deoxygenation of 1,2-Propanediol

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bullock, R.M.; Ghosh, P.; Fagan, P.J.

2009-07-20

A ruthenium hydride with a bulky tetra-substituted Cp ligand, (Cp{sup iPr{sub 4}})Ru(CO){sub 2}H (Cp{sup iPr{sub 4}} = C{sub 5}(i-C{sub 3}H{sub 7}){sub 4}H) was prepared from the reaction of Ru{sub 3}(CO){sub 12} with 1,2,3,4-tetraisopropylcyclopentadiene. The molecular structure of (Cp{sup iPr{sub 4}})Ru(CO){sub 2}H was determined by X-ray crystallography. The ruthenium hydride complex (C{sub 5}Bz{sub 5})Ru(CO){sub 2}H (Bz = CH{sub 2}Ph) was similarly prepared. The Ru-Ru bonded dimer, [(1,2,3-trimethylindenyl)Ru(CO){sub 2}]{sub 2}, was produced from the reaction of 1,2,3-trimethylindene with Ru{sub 3}(CO){sub 12}, and protonation of this dimer with HOTf gives {l_brace}[(1,2,3-trimethylindenyl)Ru(CO){sub 2}]{sub 2}-({mu}-H){r_brace}{sup +}OTf{sup -}. A series of ruthenium hydride complexes CpRu(CO)(L)H [Lmore » = P(OPh){sub 3}, PCy{sub 3}, PMe{sub 3}, P(p-C{sub 6}H{sub 4}F){sub 3}] were prepared by reaction of Cp(CO){sub 2}RuH with added L. Protonation of (Cp{sup iPr{sub 4}})Ru(CO){sub 2}H, Cp*Ru(CO){sub 2}H, or CpRu(CO)[P-(OPh){sub 3}]H by HOTf at -80 C led to equilibria with the cationic dihydrogen complexes, but H{sub 2} was released at higher temperatures. Protonation of CpRu[P(OPh){sub 3}]{sub 2}H with HOTf gave an observable dihydrogen complex, {l_brace}CpRu[P-(OPh){sub 3}]{sub 2}({eta}{sup 2}-H{sub 2}){r_brace}+OTf{sup -} that was converted at -20 C to the dihydride complex {l_brace}CpRu[P(OPh){sub 3}]{sub 2}(H){sub 2}{r_brace}{sup +}OTf{sup -}. These Ru complexes serve as catalyst precursors for the catalytic deoxygenation of 1,2-propanediol to give n-propanol. The catalytic reactions were carried out in sulfolane solvent with added HOTf under H{sub 2} (750 psi) at 110 C.« less

Effects of Coordinating a Hemilabile Ligand to 14e Cp*M(NO) Scaffolds (M = Mo, W).

PubMed

Handford, Rex C; Patrick, Brian O; Legzdins, Peter

2017-10-16

This article describes the differing chemical properties imparted by the two ligands, hemilabile 2-[(diisopropylphosphino)methyl]-3-methylpyridine ( i Pr 2 PN) and the related 1,2-bis(dimethylphosphino)ethane (dmpe), when attached to the 14e Cp*M(NO) scaffolds (Cp* = η 5 -C 5 Me 5 ; M = W, Mo). For instance, the treatment of [Cp*W(NO)Cl 2 ] 2 with 2 or 1 equiv of dmpe in C 6 H 6 affords excellent yields of [Cp*W(NO)(κ 2 -dmpe)Cl]Cl (1) or [Cp*W(NO)Cl 2 ] 2 [μ-dmpe] (2). In contrast, the treatment of [Cp*W(NO)Cl 2 ] 2 with 1 equiv of i Pr 2 PN in C 6 H 6 does not produce the complex analogous to 1 but rather affords orange [Cp*W(NO)(κ 2 -P-N- i Pr 2 PN)Cl][Cp*W(NO)Cl 3 ] (3) in 90% yield. Furthermore, subsequent reduction of 1 or 2 with 2 or 4 equiv of Cp 2 Co in tetrahydrofuran (THF), respectively, results in the production of orange Cp*W(NO)(κ 2 -dmpe) (4) in good yields. However, a similar treatment of 3 with 1 equiv of Cp 2 Co in THF does not result in the production of Cp*W(NO)(κ 2 -P,N- i Pr 2 PN), the analogue of 4, but rather generates a 1:1 mixture of the novel complexes Cp*W(NO)(H)(κ 1 -P- i Pr 2 PN)Cl (5) and Cp*W(NO)(κ 2 -P,N- i Pr 2 PCH-2-(3-Me-C 5 H 3 N))Cl (6), which are separable by crystallization from pentane and diethyl ether solutions, respectively. The divergent reactivity imparted by the dmpe and i Pr 2 PN proligands is a unique demonstration of the unusual properties of a mixed-donor ligand. In the case of molybdenum, the reaction of [Cp*Mo(NO)Cl 2 ] 2 with 2 equiv of i Pr 2 PN in C 6 H 6 first forms Cp*Mo(NO)(κ 1 -P- i Pr 2 PN)Cl 2 , which then converts to [Cp*Mo(NO)(κ 2 -P,N- i Pr 2 PN)Cl][Cp*Mo(NO)Cl 3 ], the analogue of 3. Reduction of the Cp*Mo(NO)(κ 1 -P- i Pr 2 PN)Cl 2 intermediate complex with 2 equiv of Cp 2 Co affords dark-green Cp*Mo(NO)(κ 2 -P,N- i Pr 2 PN) (7). All new complexes have been characterized by conventional spectroscopic and analytical methods, and the solid-state molecular structures of most of them have been established by single-crystal X-ray crystallographic analyses.

Structural and Electrochemical Consequences of [Cp*] Ligand Protonation.

PubMed

Peng, Yun; Ramos-Garcés, Mario V; Lionetti, Davide; Blakemore, James D

2017-09-05

There are few examples of the isolation of analogous metal complexes bearing [η 5 -Cp*] and [η 4 -Cp*H] (Cp* = pentamethylcyclopentadienyl) complexes within the same metal/ligand framework, despite the relevance of such structures to catalytic applications. Recently, protonation of Cp*Rh(bpy) (bpy = 2,2'-bipyridyl) has been shown to yield a complex bearing the uncommon [η 4 -Cp*H] ligand, rather than generating a [Rh III -H] complex. We now report the purification and isolation of this protonated species, as well as characterization of analogous complexes of 1,10-phenanthroline (phen). Specifically, reaction of Cp*Rh(bpy) or Cp*Rh(phen) with 1 equiv of Et 3 NH + Br - affords rhodium compounds bearing endo-η 4 -pentamethylcyclopentadiene (η 4 -Cp*H) as a ligand. NMR spectroscopy and single-crystal X-ray diffraction studies confirm protonation of the Cp* ligand, rather than formation of metal hydride complexes. Analysis of new structural data and electronic spectra suggests that phen is significantly reduced in Cp*Rh(phen), similar to the case of Cp*Rh(bpy). Backbonding interactions with olefinic motifs are activated by formation of [η 4 -Cp*H]; protonation of [Cp*] stabilizes the low-valent metal center and results in loss of reduced character on the diimine ligands. In accord with these changes in electronic structure, electrochemical studies reveal a distinct manifold of redox processes that are accessible in the [Cp*H] complexes in comparison with their [Cp*] analogues; these processes suggest new applications in catalysis for the complexes bearing endo-η 4 -Cp*H.

Synthesis and oxidation of CpIrIII compounds: functionalization of a Cp methyl group.

PubMed

Park-Gehrke, Lisa S; Freudenthal, John; Kaminsky, Werner; Dipasquale, Antonio G; Mayer, James M

2009-03-21

[CpIrCl(2)](2) () and new CpIr(III)(L-L)X complexes (L-L = N-O or C-N chelating ligands; X = Cl, I, Me) have been prepared and their reactivity with two-electron chemical oxidants explored. Reaction of with PhI(OAc)(2) in wet solvents yields a new chloro-bridged dimer in which each of the Cp ligands has been singly acetoxylated to form [Cp(OAc)Ir(III)Cl(2)](2) () (Cp(OAc) = eta(5)-C(5)Me(4)CH(2)OAc). Complex and related carboxy- and alkoxy-functionalized Cp(OR) complexes can also be prepared from plus (PhIO)(n) and ROH. [Cp(OAc)Ir(III)Cl(2)](2) () and the methoxy analogue [Cp(OMe)Ir(III)Cl(2)](2) () have been structurally characterized. Treatment of [CpIrCl(2)](2) () with 2-phenylpyridine yields CpIr(III)(ppy)Cl () (ppy = cyclometallated 2-phenylpyridyl) which is readily converted to its iodide and methyl analogues CpIr(III)(ppy)I and CpIr(III)(ppy)Me (). CpIr(III) complexes were also prepared with N-O chelating ligands derived from anthranilic acid (2-aminobenzoic acid) and alpha-aminoisobutyric acid (H(2)NCMe(2)COOH), ligands chosen to be relatively oxidation resistant. These complexes and were reacted with potential two-electron oxidants including PhI(OAc)(2), hexachlorocyclohexadienone (C(6)Cl(6)O), N-fluoro-2,4,6-trimethylpyridinium (Me(3)pyF(+)), [Me(3)O]BF(4) and MeOTf (OTf = triflate, CF(3)SO(3)). Iridium(V) complexes were not observed or implicated in these reactions, despite the similarity of the potential products to known CpIr(V) species. The carbon electrophiles [Me(3)O]BF(4) and MeOTf appear to react preferentially at the N-O ligands, to give methyl esters in some cases. Overall, the results indicate that Cp is not inert under oxidizing conditions and is therefore not a good supporting ligand for oxidizing organometallic complexes.

Syntheses of monomeric (. eta. sup 5 -pentamethylcyclopentadienyl)platinum(IV) methyl and bromo complexes and of (hydrotris(3,5-dimethyl-1-pyrazolyl)borato)trimethylplatinum

DOE Office of Scientific and Technical Information (OSTI.GOV)

Roth, S.; Ramamoorthy, V.; Sharp, P.R.

1990-09-05

The reaction of Cp*MgCl{center dot}THF (Cp* = C{sub 5}Me{sub 5}) with 1 equiv of PtMe{sub 3}I and PtMe{sub 2}Br{sub 2} produces Cp*PtMe{sub 3} (1) and Cp*PtMe{sub 2}Br (2), respectively. Reaction of 2 with Br{sub 2} produces Cp*PtMeBr{sub 2} (3) in good yield. The structures of 2 and 3 have been determined by x-ray crystallography, and the crystal structure data are reported. Complex 2 crystallizes in the monoclinic space group, P2{sub 1}/m, and complex 3 crystallizes in the monoclinic space group, P2{sub 1}/m. The molecules reside on mirror planes and are monomeric pseudotetrahedral Pt(IV) complexes with piano stool type geometries andmore » {eta}{sup 5}-Cp* groups. Both molecules have Br atoms on the mirror. This leads to a disorder of the Me and the second Br positions in complex 3. The average Pt-C(Cp*) bond length is 2.25 (7) {angstrom} in 2 and 2.22 (4) {angstrom} in 3. The Pt-C(Me) and Pt-Br bond lengths in 2 are 2.07 (2) and 2.498 (2) {angstrom}, respectively. The ordered Pt-Br bond length in 3 is 2.496 (2) {angstrom}. Treatment of 1 with halogens results in the cleavage of the Pt-Cp* bond. The reaction of PtMe{sub 3}I with KTp* (Tp* = (HB(3,5-dimethylpyrazolyl){sub 3}){sup {minus}}) in thf gives Tp*PtMe{sub 3} (4) in almost quantitative yield. The reaction of 4 with Br{sub 2} brominates the 4-position of the pyrazolyl ring only. 28 refs., 2 figs., 5 tabs.« less

Half-sandwich rhodium(III) transfer hydrogenation catalysts: Reduction of NAD(+) and pyruvate, and antiproliferative activity.

PubMed

Soldevila-Barreda, Joan J; Habtemariam, Abraha; Romero-Canelón, Isolda; Sadler, Peter J

2015-12-01

Organometallic complexes have the potential to behave as catalytic drugs. We investigate here Rh(III) complexes of general formula [(Cp(x))Rh(N,N')(Cl)], where N,N' is ethylenediamine (en), 2,2'-bipyridine (bpy), 1,10-phenanthroline (phen) or N-(2-aminoethyl)-4-(trifluoromethyl)benzenesulfonamide (TfEn), and Cp(x) is pentamethylcyclopentadienyl (Cp*), 1-phenyl-2,3,4,5-tetramethylcyclopentadienyl (Cp(xPh)) or 1-biphenyl-2,3,4,5-tetramethyl cyclopentadienyl (Cp(xPhPh)). These complexes can reduce NAD(+) to NADH using formate as a hydride source under biologically-relevant conditions. The catalytic activity decreased in the order of N,N-chelated ligand bpy > phen > en with Cp* as the η(5)-donor. The en complexes (1-3) became more active with extension to the Cp(X) ring, whereas the activity of the phen (7-9) and bpy (4-6) compounds decreased. [Cp*Rh(bpy)Cl](+) (4) showed the highest catalytic activity, with a TOF of 37.4±2h(-1). Fast hydrolysis of the chlorido complexes 1-10 was observed by (1)H NMR (<10min at 310K). The pKa* values for the aqua adducts were determined to be ca. 8-10. Complexes 1-9 also catalysed the reduction of pyruvate to lactate using formate as the hydride donor. The efficiency of the transfer hydrogenation reactions was highly dependent on the nature of the chelating ligand and the Cp(x) ring. Competition reactions between NAD(+) and pyruvate for reduction by formate catalysed by 4 showed a preference for reduction of NAD(+). The antiproliferative activity of complex 3 towards A2780 human ovarian cancer cells increased by up to 50% when administered in combination with non-toxic doses of formate, suggesting that transfer hydrogenation can induce reductive stress in cancer cells. Copyright © 2015 The Authors. Published by Elsevier Inc. All rights reserved.

Frustrated Lewis pairs beyond the main group: cationic zirconocene-phosphinoaryloxide complexes and their application in catalytic dehydrogenation of amine boranes.

PubMed

Chapman, Andy M; Haddow, Mairi F; Wass, Duncan F

2011-06-15

The cationic zirconocene-phosphinoaryloxide complexes [Cp(2)ZrOC(6)H(4)P(t-Bu)(2)][B(C(6)F(5))(4)] (3) and [Cp*(2)ZrOC(6)H(4)P(t-Bu)(2)][B(C(6)F(5))(4)] (4) were synthesized by the reaction of Cp(2)ZrMe(2) or Cp*(2)ZrMe(2) with 2-(diphenylphosphino)phenol followed by protonation with [2,6-di-tert-butylpyridinium][B(C(6)F(5))(4)]. Compound 3 exhibits a Zr-P bond, whereas the bulkier Cp* derivative 4 was isolated as a chlorobenzene adduct without this Zr-P interaction. These compounds can be described as transition-metal-containing versions of linked frustrated Lewis pairs (FLPs), and treatment of 4 with H(2) under mild conditions cleaved H(2) in a fashion analogous to that for main-group FLPs. Their reactivity in amine borane dehydrogenation also mimics that of main-group FLPs, and they dehydrogenate a range of amine borane adducts. However, in contrast to main-group FLPs, 3 and 4 achieve this transformation in a catalytic rather than stoichiometric sense, with rates superior to those for previous high-valent catalysts. © 2011 American Chemical Society

A halogenophilic pathway in the reactions of transition metal carbonyl anions with [(η⁶-iodobenzene)Cr(CO)₃].

PubMed

Sazonov, Petr K; Ivushkin, Vasiliy A; Khrustalev, Victor N; Kolotyrkina, Natal'ya G; Beletskaya, Irina P

2014-09-21

The paper provides the first example of formal nucleophilic substitution by the halogenophilic pathway in Cr(CO)3 complexes of haloarenes with metal carbonyl anions. All metal carbonyl anions examined attack [(η(6)-iodobenzene)Cr(CO)3] at halogen, which is shown by aryl carbanion scavenging with t-BuOH. The reaction with K[CpFe(CO)2] gives only the dehalogenated arene, but the reaction with K[Cp*Fe(CO)2] (Cp* = η(5)-C5Me5) results in nucleophilic substitution to give [(η(6)-C6H5FeCp*(CO)2)Cr(CO)3]. Reaction with Na[Re(CO)5] quantitatively gives the iodo(acyl)rhenate anion Na[(η(6)-C6H5C(O)ReI(CO)4)Cr(CO)3] and in the case of K[Mn(CO)5] a mixture of σ-aryl complexes [(η(6)-C6H5Mn(CO)5)Cr(CO)3] and K[(η(6)-C6H5Mn(CO)4I)Cr(CO)3]. An analogous rhenium complex Na[(η(6)-C6H5Re(CO)4I)Cr(CO)3] is formed from the initial iodo(acyl)rhenate upon prolonged standing at 20 °C, and its structure (in the form of [NEt4](+) salt) is established by X-ray diffraction analysis. The reaction of [(η(6)-chlorobenzene)Cr(CO)3] with K[CpFe(CO)2], in contrast, proceeds by the common S(N)2Ar mechanism.

Degradation kinetics of chlorpyrifos and 3,5,6-trichloro-2-pyridinol (TCP) by fungal communities.

PubMed

Maya, K; Upadhyay, S N; Singh, R S; Dubey, Suresh K

2012-12-01

Fungal isolates obtained from soil were used for degrading chlorpyrifos (CP) and TCP. The percentage degradation ranged from 69.4 to 89.8 for CP and 62.2 to 92.6 for TCP after one week. The values of K(s) and V(max) were different for different isolates. The K(s) ranged from 66.66 to 169.5mg/L and V(max) from 6.56 to 40.4 mg/L/d for CP and from 53.19 to 163.9 mg/L and 3.41 to 40.40 mg/L/d, respectively, for TCP. Fungal community showed high affinity for both CP and TCP. The genetic relatedness of isolate F1 to Aspergillus sp., F2 and F3 to Penicillium sp., F4 to Eurotium sp. and F5 to Emericella sp. were confirmed. The degradation potential was in the order: F1>F2=F3>F4>F5. Copyright © 2012 Elsevier Ltd. All rights reserved.

Effects of Static or Oscillating Dietary Crude Protein Levels on Fermentation Dynamics of Beef Cattle Diets Using a Dual-Flow Continuous Culture System

PubMed Central

Benedeti, Pedro Del Bianco; da Silva, Lorrayny Galoro; de Paula, Eduardo Marostegan; Monteiro, Hugo Fernando; Shenkoru, Teshome; Santos, Stefanie Alvarenga; Poulson, Simon Roger

2016-01-01

The objective of this study was to evaluate the effects of increasing dietary crude protein (CP) levels and also comparing the effects of static versus oscillating dietary CP on ruminal nutrient digestibility, ruminal fermentation, nitrogen (N) metabolism, and microbial efficiency in beef cattle diets using a dual-flow continuous culture system. Eight fermenters (1,223 ± 21 mL) were used in a replicated 4 x 4 Latin square design with periods lasting 12 d each (8 d for adaptation and 4 d for sampling). Dietary treatments were: 1) 10% CP, 2) 12% CP, 3) 14% CP, and 4) 10 and 14% CP diets oscillating at 48-h intervals. Experimental diets consisted of 50% orchard hay and 50% concentrate. Fermenters were fed 72 g/d and solid and liquid dilution rates were adjusted to 5.5 and 11%/h, respectively. Data were analyzed using the MIXED procedure in SAS with α = 0.05. Apparent and true ruminal digestibilities of dry matter and organic matter were not affected (P > 0.05) by increasing dietary CP, nor by oscillating dietary CP. Total volatile fatty acids concentration and molar proportions of acetate, propionate, butyrate, valerate, iso-butyrate and iso-valerate were not affected (P > 0.05) by increasing or oscillating dietary CP. Ruminal NH3-N concentration increased linearly (P < 0.01) in response to increasing dietary CP. Total N, non-ammonia N, and rumen undegraded protein flows did not differ among treatments or between oscillating dietary CP and static 12% CP. Microbial N and NH3-N flows and microbial efficiency did not differ when comparing oscillating versus static CP (P > 0.05). However, there was a quadratic effect (P < 0.05) for these variables when dietary CP was increased. These results indicate that either ruminal microorganisms do not respond to oscillating CP levels or are capable of coping with 48-h periods of undernourishment. PMID:28036405

Identification of two novel mammalian genes establishes a subfamily of KH-domain RNA-binding proteins.

PubMed

Makeyev, A V; Liebhaber, S A

2000-08-01

We have identified two novel human genes encoding proteins with a high level of sequence identity to two previously characterized RNA-binding proteins, alphaCP-1 and alphaCP-2. Both of these novel genes, alphaCP-3 and alphaCP-4, are predicted to encode proteins with triplicated KH domains. The number and organization of the KH domains, their sequences, and the sequences of the contiguous regions are conserved among all four alphaCP proteins. The common evolutionary origin of these proteins is substantiated by conservation of exon-intron organization in the corresponding genes. The map positions of alphaCP-1 and alphaCP-2 (previously reported) and those of alphaCP-3 and alphaCP-4 (present report) reveal that the four alphaCP loci are dispersed in the human genome; alphaCP-3 and alphaCP-4 mapped to 21q22.3 and 3p21, and the respective mouse orthologues mapped to syntenic regions of the mouse genome, 10B5 and 9F1-F2, respectively. Two additional loci in the human genome were identified as alphaCP-2 processed pseudogenes (PCBP2P1, 21q22.3, and PCBP2P2, 8q21-q22). Although the overall levels of alphaCP-3 and alphaCP-4 mRNAs are substantially lower than those of alphaCP-1 and alphaCP-2, transcripts of alphaCP-3 and alphaCP-4 were found in all mouse tissues tested. These data establish a new subfamily of genes predicted to encode closely related KH-containing RNA-binding proteins with potential functions in posttranscriptional controls. Copyright 2000 Academic Press.

Protective immunity against Megalocytivirus infection in rock bream (Oplegnathus fasciatus) following CpG ODN administration.

PubMed

Jung, Myung-Hwa; Lee, Jehee; Ortega-Villaizan, M; Perez, Luis; Jung, Sung-Ju

2017-06-27

Rock bream iridovirus (RBIV) disease in rock bream (Oplegnathus fasciatus) remains an unsolved problem in Korea aquaculture farms. CpG ODNs are known as immunostimulant, can improve the innate immune system of fish providing resistance to diseases. In this study, we evaluated the potential of CpG ODNs to induce anti-viral status protecting rock bream from different RBIV infection conditions. We found that, when administered into rock bream, CpG ODN 1668 induces better antiviral immune responses compared to other 5 CpG ODNs (2216, 1826, 2133, 2395 and 1720). All CpG ODN 1668 administered fish (1/5µg) at 2days before infection (1.1×10 7 ) held at 26°C died even though mortality was delayed from 8days (1µg) and 4days (5µg). Similarly, CpG ODN 1668 administered (5µg) at 2days before infection (1.2×10 6 ) held at 23/20°C had 100% mortality; the mortality was delayed from 9days (23°C) and 11days (20°C). Moreover, when CpG ODN 1668 administered (1/5/10µg) at 2/4/7days before infection or virus concentration was decreased to 1.1×10 4 and held at 20°C had mortality rates of 20/60/30% (2days), 30/40/60% (4days) and 60/60/20% (7days), respectively, for the respective administration dose, through 100 dpi. To investigate the development of a protective immune response, survivors were re-infected with RBIV (1.1×10 7 ) at 100 and 400 dpi, respectively. While 100% of the previously unexposed fish died, 100% of the previously infected fish survived. The high survival rate of fish following re-challenge with RBIV indicates that protective immunity was established in the surviving rock bream. Our results showed the possibility of developing preventive measures against RBIV using CpG ODN 1668 by reducing RBIV replication speed (i.e. water temperature of 20°C and infection dose of 1.1×10 4 ). Copyright © 2017 Elsevier Ltd. All rights reserved.

Search for CP violation in singly Cabibbo suppressed four-body D decays

DOE Office of Scientific and Technical Information (OSTI.GOV)

Martinelli, Maurizio

2011-02-01

We search for CP violation in a sample of 4.7 x 10 4 singly Cabibbo suppressed D 0 → K + K - π +π - decays and 1.8(2.6) x 10 4 D (s) + → K S 0 K + π + π - decays. CP violation is searched for in the difference between the T-odd asymmetries, obtained using triple product correlations, measured for D and D decays. The measured CP violation parameters are A T(D 0) = (1.0 ± 5.1(stat) ± 4.4(syst)) x 10 -3, A T(D +) = (-11.96 ± 10.04(stat) ± 4.81(syst)) x 10 -3 andmore » A T(D s +) = (-13.57 ± 7.67(stat) ± 4.82(syst)) x 10 -3. This search for CP violation showed that the T-odd correlations are a powerful tool to measure the CP violating observable A T. The relative simplicity of an analysis based on T-odd correlations and the high quality results that can be obtained, allow to consider this tool as fundamental to search for CP violation in four-body decays. Even if the CP violation has not been found, excluding any New Physics effect to the sensitivity of about 0.5%, it is still worth to search for CP violation in D decays. The high statistics that can be obtained at the LHC or by the proposed high luminosity B-factories, make this topic to be considered in high consideration by experiments such as LHCb, SuperB or SuperBelle. The results outlined in this thesis strongly suggest to include a similar analysis into the Physics program of these experiments.« less

Effect of a low crude protein diet supplemented with different levels of threonine on growth performance, carcass traits, blood parameters, and immune responses of growing broilers.

PubMed

Sigolo, Samantha; Zohrabi, Zahra; Gallo, Antonio; Seidavi, Alireza; Prandini, Aldo

2017-08-01

A study was conducted to evaluate growth performance, carcass traits, blood serum parameters, and immune responses of Ross 308 male broilers fed diets containing 2 different crude protein (CP) levels (97.5 and 100%) and 4 threonine (Thr) levels (100, 110, 120, and 130% of Ross recommendations for starter and grower periods). A completely randomized block design was adopted and main effects (CP and Thr) were arranged in a 2 × 4 factorial approach. Optimum growth performance was achieved when broiler requirements for CP and Thr were 100% satisfied. The 110% Thr inclusion in 97.5% CP diet increased ADG, ADFI, energy intake, and protein intake (Thr, P < 0.01; quadratic, P = 0.01). The G:F (linear, P = 0.05) and energy efficiency (linear, P = 0.04) tended to decreased (Thr, P = 0.09) by increasing Thr supplementation level, whereas protein efficiency tended to increase (CP, P = 0.06) by reducing CP level. The 110% Thr inclusion in 97.5% CP diet increased eviscerated carcass weight (CP × Thr, P = 0.03) and carcass yield (Thr, P = 0.08; quadratic, P = 0.05). The reduction of CP content promoted fat abdominal deposition (CP, P = 0.05). Incremental Thr raised abdominal fat (Thr, P = 0.01; linear, P = 0.01). The 97.5% CP diets resulted in higher serum concentrations of uric acid (CP, P = 0.02), total and high- and low-density lipoprotein-linked cholesterol (CP, P≤ 0.01), and alanine aminotransferase (CP, P = 0.05) and lower (CP, P = 0.01) concentrations of triglycerides and very low density lipoproteins compared with the 100% CP diets. However, the Thr inclusion improved serum lipid profile. Irrespective of CP content, incremental Thr levels up to 120% increased (Thr, P = 0.01) broiler immune responses against Newcastle disease virus and sheep red blood cells. In order to reduce dietary CP content, strategies to increase synthetic amino acid availability, such as the use of encapsulated amino acids, should be taken into account. © 2017 Poultry Science Association Inc.

Intramolecular mobility of η(5)-ligands in chiral zirconocene complexes and the enantioselectivity of alkene functionalization by organoaluminum compounds.

PubMed

Parfenova, Lyudmila V; Zakirova, Irina V; Kovyazin, Pavel V; Karchevsky, Stanislav G; Istomina, Galina P; Khalilov, Leonard M; Dzhemilev, Usein M

2016-08-09

The effect of solvent nature (CD2Cl2, d8-toluene, d8-THF) on the conformational behavior of neomenthyl-substituted zirconocenes CpInd*ZrCl2 (Cp = η(5)-C5H5, Ind* = η(5)-neomenthylindenyl), CpCp'ZrCl2 (Cp = η(5)-C5H5, Cp' = η(5)-neomenthyl-4,5,6,7-tetrahydroindenyl), and Ind*2ZrCl2 (Ind* = η(5)-neomenthylindenyl) was shown by means of dynamic NMR spectroscopy, and the constants and thermodynamic parameters of conformer exchange were determined. The experimental conformational composition of the complexes was compared with structures obtained by quantum chemical modeling using the DFT methods PBE/3ζ and M06-2X/cc-pVDZ(H, C, Cl)/cc-pVDZ-PP(Zr), which predicted three rotamers in the case of both CpInd*ZrCl2 and CpCp'ZrCl2, and seven rotational isomers for Ind*2ZrCl2, three of these being C2-symmetric and the others being asymmetric. The enantioselectivity of the conformationally mobile complex Ind*2ZrCl2 in the reactions of terminal alkenes with AlR3 (R = Me, Et) was compared with that of rigid ansa-complexes, rac-p-S, p-S-[Y(η(5)-C9H10)2]ZrX2 (Y = SiMe2, C2H4; X = S-binaphtholate). Faster exchange between the conformers of Ind*2ZrCl2 in a chlorinated solvent gives the structural isomer of catalytically active sites, which affords higher substrate conversion and reaction enantioselectivity. Binding of the ligands to ansa-zirconocenes prevents the rotational isomerism of the complexes, providing the same configuration of the β-stereogenic center in the methyl- and ethylalumination products (unlike the conformationally mobile complex Ind*2ZrCl2) with an enantiomeric purity of 50-65%.

Uranyl Coordination Polymers Incorporating η5-Cyclopentadienyliron-Functionalized η6-Phthalate Metalloligands: Syntheses, Structures and Photophysical Properties

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kerr, Andrew T.; Kumalah, Sayon A.; Holman, K. T.

2013-10-06

The reaction of two η5-cyclopentadienyliron(II)-functionalized terephthalate and phthalate metalloligands, namely [(η5-C5H5)FeII(η6-1,4-HO2CC6H4CO2H)][(η5-C5H5)FeII(η6-1,4-HO2CC6H4CO2)][PF6] and [(η5-C5H5)FeII(η6-1,2-HO2CC6H4CO2H)][(η5-C5H5)FeII(η6-1,2-HO2CC6H4CO2)][PF6]—hereafter [H2 CpFeTP][HCpFeTP][PF6] and [H2 CpFeP][HCpFeP][PF6], respectively—with [UO2(NO3)2]·6H2O under hydrothermal conditions yielded four new coordination polymers; (1) [(UO2)F(HCpFeTP)(PO4H2)]·2H2O, (2) [(UO2)2(CpFeTP)4]·5H2O, (3) [(UO2)2F3(H2O)(CpFeP)], and (4) [H2 CpFeP][UO2F3]. The use of metalloligands has proven to be a viable route towards the incorporation of a secondary metal center into uranyl bearing materials. Depending upon the protonation state, the iron sandwich metalloligands may vary from zwitterionic neutral or monoanionic coordinating species as observed in compounds 1–3, or a positively charged species that hydrogen bonds with anionic [UO2F3]- chains as observed in 4.more » Further, the hydrolysis of the charge balancing PF6 - anion increases the diversity of UO2 2+ coordinating species by contributing both F- and PO4 3- anions (1, 3, 4). The luminescent properties of 1–4 were also studied and revealed the absence of uranyl emission, suggestive of a possible energy transfer from the uranyl cation to the iron(II) metal center.« less

Effects of rumen undegradable protein supplementation on productive performance and indicators of protein and energy metabolism in Holstein fresh cows.

PubMed

Amanlou, H; Farahani, T Amirabadi; Farsuni, N Eslamian

2017-05-01

The objective of this study was to determine the effects of feeding increased dietary crude protein (CP) on productive performance and indicators of protein and energy metabolism during 21 d postpartum. Thirty multiparous Holstein dairy cows were balanced by previous lactation milk yield, body condition score (BCS) at calving, and parity and randomly allocated to 1 of 3 dietary treatments from calving until 21 d postpartum. Dietary treatments were 16.0% CP with 5.0% rumen undegradable protein (RUP) based on dry matter (DM) (16CP), 18.7% CP with 7.0% RUP based on DM (19CP), and 21.4% CP with 9.0% RUP based on DM (21CP). Diets were similar in net energy for lactation (approximately 1.7 Mcal/kg of DM) and CP levels were increased with corn gluten meal and fish meal. Dry matter intake (DMI) was increased by increasing dietary CP levels from 16.0 to 19.0% of DM, but dietary CP beyond 19.0% had no effect on DMI. Milk yields were 4.7 and 6.5 kg/d greater in cows fed the 19CP and 21CP diets versus those fed the 16CP diet, whereas 4% fat-corrected milk was greater for cows fed the 21CP than the 16CP diet (36.0 vs. 31.4 kg/d). Milk protein content and yield, lactose yield, and milk urea nitrogen were elevated by increased dietary CP. Milk lactose content and fat yield were not different among dietary treatments, but milk fat content tended to decline with increasing content of CP in diets. High CP levels increased milk N secretion but decreased milk N efficiency. Apparent digestibility of DM, CP, and neutral detergent fiber was greater on the 19CP and 21CP diets compared with the 16CP diet. Cows fed the 19CP and 21CP diets lost less body condition relative to those fed the 16CP diet over 21 d postpartum. Feeding higher CP levels increased the concentrations of serum albumin, albumin to globulin ratio, and urea nitrogen and decreased aspartate aminotransferase, nonesterified fatty acids, and β-hydroxybutyrate, but had no effect on globulin, glucose, cholesterol, or triacylglycerol. These findings indicated that elevating dietary CP up to 19.0% of DM using RUP supplements improved DMI, productive performance and the indicators of protein and energy metabolism from calving to 21 d postpartum. Copyright © 2017 American Dairy Science Association. Published by Elsevier Inc. All rights reserved.

7-Carboxy-7-deazaguanine Synthase: A Radical S-Adenosyl-l-methionine Enzyme with Polar Tendencies

PubMed Central

2017-01-01

Radical S-adenosyl-l-methionine (SAM) enzymes are widely distributed and catalyze diverse reactions. SAM binds to the unique iron atom of a site-differentiated [4Fe-4S] cluster and is reductively cleaved to generate a 5′-deoxyadenosyl radical, which initiates turnover. 7-Carboxy-7-deazaguanine (CDG) synthase (QueE) catalyzes a key step in the biosynthesis of 7-deazapurine containing natural products. 6-Carboxypterin (6-CP), an oxidized analogue of the natural substrate 6-carboxy-5,6,7,8-tetrahydropterin (CPH4), is shown to be an alternate substrate for CDG synthase. Under reducing conditions that would promote the reductive cleavage of SAM, 6-CP is turned over to 6-deoxyadenosylpterin (6-dAP), presumably by radical addition of the 5′-deoxyadenosine followed by oxidative decarboxylation to the product. By contrast, in the absence of the strong reductant, dithionite, the carboxylate of 6-CP is esterified to generate 6-carboxypterin-5′-deoxyadenosyl ester (6-CP-dAdo ester). Structural studies with 6-CP and SAM also reveal electron density consistent with the ester product being formed in crystallo. The differential reactivity of 6-CP under reducing and nonreducing conditions highlights the ability of radical SAM enzymes to carry out both polar and radical transformations in the same active site. PMID:28045519

7-Carboxy-7-deazaguanine Synthase: A Radical S -Adenosyl- l -methionine Enzyme with Polar Tendencies

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bruender, Nathan A.; Grell, Tsehai A. J.; Dowling, Daniel P.

Radical S-adenosyl-l-methionine (SAM) enzymes are widely distributed and catalyze diverse reactions. SAM binds to the unique iron atom of a site-differentiated [4Fe-4S] cluster and is reductively cleaved to generate a 5'-deoxyadenosyl radical, which initiates turnover. 7-Carboxy-7-deazaguanine (CDG) synthase (QueE) catalyzes a key step in the biosynthesis of 7-deazapurine containing natural products. 6-Carboxypterin (6-CP), an oxidized analogue of the natural substrate 6-carboxy-5,6,7,8-tetrahydropterin (CPH4), is shown to be an alternate substrate for CDG synthase. Under reducing conditions that would promote the reductive cleavage of SAM, 6-CP is turned over to 6-deoxyadenosylpterin (6-dAP), presumably by radical addition of the 5'-deoxyadenosine followed by oxidativemore » decarboxylation to the product. By contrast, in the absence of the strong reductant, dithionite, the carboxylate of 6-CP is esterified to generate 6-carboxypterin-5'-deoxyadenosyl ester (6-CP-dAdo ester). Structural studies with 6-CP and SAM also reveal electron density consistent with the ester product being formed in crystallo. The differential reactivity of 6-CP under reducing and nonreducing conditions highlights the ability of radical SAM enzymes to carry out both polar and radical transformations in the same active site.« less

Naphthoquinone spiroketals and organic extracts from the endophytic fungus Edenia gomezpompae as potential herbicides.

PubMed

Macías-Rubalcava, Martha L; Ruiz-Velasco Sobrino, M Emma; Meléndez-González, Claudio; Hernández-Ortega, Simón

2014-04-23

From the fermentation mycelium of the endophytic fungus Edenia gomezpompae were obtained several phytotoxic compounds including two new members of the naphthoquinone spiroketal family, namely, palmarumycin EG1 (1) and preussomerin EG4 (4). In addition, preussomerins EG1-EG3 (7-9) and palmarumycins CP19 (2), CP17 (3), and CP2 (6), as well as ergosta-4,6,8(14),22-tetraen-3-one (5), were obtained. Compounds 2, 3, and 5 are new to this species. The structures of palmarumycins CP19 (2) and CP17 (3) were unambiguously determined by X-ray analysis. The isolates and mycelium organic extracts from four morphological variants of E. gomezpompae caused significant inhibition of seed germination, root elongation, and seedling respiration of Amaranthus hypochondriacus, Solanum lycopersicum, and Echinochloa crus-galli. The treatments also affected respiration on intact mitochondria isolated from spinach.

Craniopharyngioma adherence: a comprehensive topographical categorization and outcome-related risk stratification model based on the methodical examination of 500 tumors.

PubMed

Prieto, Ruth; Pascual, José María; Rosdolsky, Maria; Castro-Dufourny, Inés; Carrasco, Rodrigo; Strauss, Sewan; Barrios, Laura

2016-12-01

OBJECTIVE Craniopharyngioma (CP) adherence strongly influences the potential for achieving a radical and safe surgical treatment. However, this factor remains poorly addressed in the scientific literature. This study provides a rational, comprehensive description of CP adherence that can be used for the prediction of surgical risks associated with the removal of these challenging lesions. METHODS This study retrospectively analyzes the evidence provided in pathological, neuroradiological, and surgical CP reports concerning 3 components of the CP attachment: 1) the intracranial structures attached to the tumor; 2) the morphology of the adhesion; and 3) the adhesion strength. From a total of 1781 CP reports published between 1857 and 2016, a collection of 500 CPs providing the best information about the type of CP attachment were investigated. This cohort includes autopsy studies (n = 254); surgical studies with a detailed description or pictorial evidence of CP adherence (n = 298); and surgical CP videos (n = 61) showing the technical steps for releasing the attachment. A predictive model of CP adherence in hierarchical severity levels correlated with surgical outcomes was generated by multivariate analysis. RESULTS The anatomical location of the CP attachment occurred predominantly at the third ventricle floor (TVF) (54%, n = 268), third ventricle walls (23%, n = 114), and pituitary stalk (19%, n = 94). The optic chiasm was involved in 56% (n = 281). Six morphological patterns of CP attachment were identified: 1) fibrovascular pedicle (5.4%); 2) sessile or patch-like (21%); 3) cap-like (over the CP top, 14%); 4) bowl-like (around the CP bottom, 13.5%); 5) ring-like (encircling central band, 19%); and 6) circumferential (enveloping the entire CP, 27%). Adhesion strength was classified in 4 grades: 1) loose (easily dissectible, 8%); 2) tight (requires sharp dissection, 32%); 3) fusion (no clear cleavage plane, 40%); and 4) replacement (loss of brain tissue integrity, 20%). The types of CP attachment associated with the worst surgical outcomes are the ring-like, bowl-like, and circumferential ones with fusion to the TVF or replacement of this structure (p < 0.001). The CP topography is the variable that best predicts the type of CP attachment (p < 0.001). Ring-like and circumferential attachments were observed for CPs invading the TVF (secondary intraventricular CPs) and CPs developing within the TVF itself (infundibulo-tuberal CPs). Brain invasion and peritumoral gliosis occurred predominantly in the ring-like and circumferential adherence patterns (p < 0.001). A multivariate model including the variables CP topography, tumor consistency, and the presence of hydrocephalus, infundibulo-tuberal syndrome, and/or hypothalamic dysfunction accurately predicts the severity of CP attachment in 87% of cases. CONCLUSIONS A comprehensive descriptive model of CP adherence in 5 hierarchical levels of increased severity-mild, moderate, serious, severe, and critical-was generated. This model, based on the location, morphology, and strength of the attachment can be used to anticipate the surgical risk of hypothalamic injury and to plan the degree of removal accordingly.

Cationic and Neutral Cp*M(NO)(κ2-Ph2PCH2CH2PPh2) Complexes of Molybdenum and Tungsten: Lewis-Acid-Induced Intramolecular C-H Activation.

PubMed

Handford, Rex C; Wakeham, Russell J; Patrick, Brian O; Legzdins, Peter

2017-03-20

Treatment of CH 2 Cl 2 solutions of Cp*M(NO)Cl 2 (Cp* = η 5 -C 5 (CH 3 ) 5 ; M = Mo, W) first with 2 equiv of AgSbF 6 in the presence of PhCN and then with 1 equiv of Ph 2 PCH 2 CH 2 PPh 2 affords the yellow-orange salts [Cp*M(NO)(PhCN)(κ 2 -Ph 2 PCH 2 CH 2 PPh 2 )](SbF 6 ) 2 in good yields (M = Mo, W). Reduction of [Cp*M(NO)(PhCN)(κ 2 -Ph 2 PCH 2 CH 2 PPh 2 )](SbF 6 ) 2 with 2 equiv of Cp 2 Co in C 6 H 6 at 80 °C produces the corresponding 18e neutral compounds, Cp*M(NO)(κ 2 -Ph 2 PCH 2 CH 2 PPh 2 ) which have been isolated as analytically pure orange-red solids. The addition of 1 equiv of the Lewis acid, Sc(OTf) 3 , to solutions of Cp*M(NO)(κ 2 -Ph 2 PCH 2 CH 2 PPh 2 ) at room temperature results in the immediate formation of thermally stable Cp*M(NO→Sc(OTf) 3 )(H)(κ 3 -(C 6 H 4 )PhPCH 2 CH 2 PPh 2 ) complexes in which one of the phenyl substituents of the Ph 2 PCH 2 CH 2 PPh 2 ligands has undergone intramolecular orthometalation. In a similar manner, addition of BF 3 produces the analogous Cp*M(NO→BF 3 )(H)(κ 3 -(C 6 H 4 )PhPCH 2 CH 2 PPh 2 ) complexes. In contrast, B(C 6 F 5 ) 3 forms the 1:1 Lewis acid-base adducts, Cp*M(NO→B(C 6 F 5 ) 3 )(κ 2 -Ph 2 PCH 2 CH 2 PPh 2 ) in CH 2 Cl 2 at room temperature. Upon warming to 80 °C, Cp*Mo(NO→B(C 6 F 5 ) 3 )(κ 2 -Ph 2 PCH 2 CH 2 PPh 2 ) converts cleanly to the orthometalated product Cp*Mo(NO→B(C 6 F 5 ) 3 )(H)(κ 3 -(C 6 H 4 )PhPCH 2 CH 2 PPh 2 ), but Cp*W(NO→B(C 6 F 5 ) 3 )(κ 2 -Ph 2 PCH 2 CH 2 PPh 2 ) generates a mixture of products whose identities remain to be ascertained. Attempts to extend this chemistry to include related Ph 2 PCH 2 PPh 2 compounds have had only limited success. All new complexes have been characterized by conventional spectroscopic and analytical methods, and the solid-state molecular structures of most of them have been established by single-crystal X-ray crystallographic analyses.

The in vivo pharmacology of CP-80, 633, a selective inhibitor of phosphodiesterase 4.

PubMed

Turner, C R; Cohan, V L; Cheng, J B; Showell, H J; Pazoles, C J; Watson, J W

1996-09-01

The following studies were conducted to characterize the bron-chodilatory and antiinflammatory activity of the novel, selective phosphodiesterase-IV inhibitor, CP-80,633 (2'S)5-[3-(2'-exobicyclo[2.2.1]heptyloxy-4-methoxy-phenyl]te trahydro- 2(1H)-pyrimidone, a compound in clinical development for atopic disease. In IgG1 passively sensitized guinea pigs, aerosolized ovalbumin challenge increases both pulmonary eosinophil peroxidase levels and airway obstruction. CP-80,633, administered before ovalbumin challenge, significantly attenuated both the increase in tissue eosinophil peroxidase levels (ED50 = 1.4 mg/kg, p.o.) and airway obstruction (ED50 = 0.93 +/- 0.14 mg/kg,p.o.) 10 to 30 times more potently than theophyl-line. Intraarterially administered CP-80,633 also reversed an established bronchoconstriction initiated by continuous infusion of histamine to guinea pigs (ED50 of 8.2 micrograms/kg vs. 5.6 mg/kg for theophylline). The antiinflammatory effect of CP-80,633 was also examined in atopic monkeys challenged with Ascaris suum (Ag) aerosol. CP-80,633 (1 mg/kg, qid, s.c., 1 hr before antigen challenge) significantly reduced antigen-induced increases in bronchoalveolar lavage neutrophils (72.8 +/- 15.8% inhibition) and eosinophils (61.1 +/- 5.7% inhibition) 4 hr postchallenge, but did not reduce leukocytes 24 hr postchallenge. CP-80,633 did not inhibit antigen-induced increases in BAL levels of interleukin-1 beta, -6 or -8 as measured by enzyme-linked immunosorbant assay. These results indicate that CP-80,633 possesses bronchodilatory activity in guinea pigs and some antiinflammatory effects in both guinea pigs and monkeys.

The risk of fractures among patients with cirrhosis or chronic pancreatitis.

PubMed

Bang, Ulrich Christian; Benfield, Thomas; Bendtsen, Flemming; Hyldstrup, Lars; Beck Jensen, Jens-Erik

2014-02-01

Cirrhosis and chronic pancreatitis (CP) are accompanied by inflammation and malnutrition. Both conditions can have negative effects on bone metabolism and promote fractures. We evaluated the risk of fractures among patients with CP or cirrhosis and determined the effect of fat malabsorption on fracture risk among patients with CP. We performed a retrospective cohort study using the Danish National Patient Register to identify patients diagnosed with CP or cirrhosis. We analyzed data collected from January 1, 1995, to December 31, 2010, on 20,769 patients (35.5% women with cirrhosis and 11,972 patients (33.5% women) with CP. Each patient was compared with 10 age- and sex-matched controls. We also assessed the risk of fractures among patients with CP who received pancreatic enzyme substitution (PES) for fat malabsorption. During the study period, bone fractures occurred in 3954 patients with cirrhosis and 2594 patients with CP. The adjusted hazard ratio (HR) for any fracture was 2.4 in patients with cirrhosis (95% confidence interval [CI], 2.2-2.5) and 1.7 in patients with CP (95% CI, 1.6-1.8). The relative risk of low-trauma fractures was highest among individuals younger than 50 years old. Alcohol as an etiology was associated with an increased risk of fracture compared with patients with nonalcoholic cirrhosis (HR, 2.4 vs 1.5; P < .0001) and CP (HR, 2.0 vs 1.5; P < .0001). Patients with CP receiving PES for fat malabsorption had a lower risk of fractures than other CP patients (HR, 0.8; 95% CI, 0.7-0.9). However, increasing the duration of treatment with PES was associated with an increased risk of fracture. Patients, especially younger patients, with cirrhosis or CP have an increased risk of fractures of all types. Copyright © 2014 AGA Institute. Published by Elsevier Inc. All rights reserved.

Biodegradability of Chlorophenols in Surface Waters from the Urban Area of Buenos Aires.

PubMed

Gallego, A; Laurino Soulé, J; Napolitano, H; Rossi, S L; Vescina, C; Korol, S E

2018-04-01

Biodegradability of 2-Chlorophenol (2-CP), 3-Chlorophenol (3-CP), 4-Chlorophenol (4-CP), 2,4-Dichlorophenol (2,4-DCP) and 2,4,6 Trichlorophenol (2,4,6-TCP) has been tested in surface waters in the urban area of Buenos Aires. Samples were taken from the La Plata River and from the Reconquista and Matanza-Riachuelo basins, with a total amount of 18 sampling points. Water quality was established measuring chemical oxygen demand (COD), biochemical oxygen demand (BOD 5 ), and both Escherichia coli and Enterococcus counts. Biodegradability was carried out by a respirometric method, using a concentration of 20 mg L -1 of chlorophenol, and the surface water as inoculum. Chlorophenols concentration in the same water samples were simultaneously measured by a solid phase microextraction (SPME) procedure followed by gas chromatography-mass spectrometry (GC-MS). 2,4-DCP was the most degradable compound followed by 2,4,6-TCP, 4-CP, 3-CP and 2-CP. Biodegradability showed no correlation with compound concentration. At most sampling points the concentration was below the detection limit for all congeners. Biodegradability does not correlate even with COD, BOD 5 , or fecal contamination. Biodegradability assays highlighted information about bacterial exposure to contaminants that parameters routinely used for watercourse characterization do not reveal. For this reason, they might be a helpful tool to complete the characterization of a site.

Controlling microbial contamination during hydrolysis of AFEX-pretreated corn stover and switchgrass: Effects on hydrolysate composition, microbial response and fermentation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Serate, Jose; Xie, Dan; Pohlmann, Edward

Microbial conversion of lignocellulosic feedstocks into biofuels remains an attractive means to produce sustainable energy. It is essential to produce lignocellulosic hydrolysates in a consistent manner in order to study microbial performance in different feedstock hydrolysates. Because of the potential to introduce microbial contamination from the untreated biomass or at various points during the process, it can be difficult to control sterility during hydrolysate production. In this study, we compared hydrolysates produced from AFEX-pretreated corn stover and switchgrass using two different methods to control contamination: either by autoclaving the pretreated feedstocks prior to enzymatic hydrolysis, or by introducing antibiotics duringmore » the hydrolysis of non-autoclaved feedstocks. We then performed extensive chemical analysis, chemical genomics, and comparative fermentations to evaluate any differences between these two different methods used for producing corn stover and switchgrass hydrolysates. Autoclaving the pretreated feedstocks could eliminate the contamination for a variety of feedstocks, whereas the antibiotic gentamicin was unable to control contamination consistently during hydrolysis. Compared to the addition of gentamicin, autoclaving of biomass before hydrolysis had a minimal effect on mineral concentrations, and showed no significant effect on the two major sugars (glucose and xylose) found in these hydrolysates. However, autoclaving elevated the concentration of some furanic and phenolic compounds. Chemical genomics analyses using Saccharomyces cerevisiae strains indicated a high correlation between the AFEX-pretreated hydrolysates produced using these two methods within the same feedstock, indicating minimal differences between the autoclaving and antibiotic methods. Comparative fermentations with S. cerevisiae and Zymomonas mobilis also showed that autoclaving the AFEX-pretreated feedstocks had no significant effects on microbial performance in these hydrolysates. In conclusion, our results showed that autoclaving the pretreated feedstocks offered advantages over the addition of antibiotics for hydrolysate production. The autoclaving method produced a more consistent quality of hydrolysate.« less

Controlling microbial contamination during hydrolysis of AFEX-pretreated corn stover and switchgrass: Effects on hydrolysate composition, microbial response and fermentation

DOE PAGES

Serate, Jose; Xie, Dan; Pohlmann, Edward; ...

2015-11-14

Microbial conversion of lignocellulosic feedstocks into biofuels remains an attractive means to produce sustainable energy. It is essential to produce lignocellulosic hydrolysates in a consistent manner in order to study microbial performance in different feedstock hydrolysates. Because of the potential to introduce microbial contamination from the untreated biomass or at various points during the process, it can be difficult to control sterility during hydrolysate production. In this study, we compared hydrolysates produced from AFEX-pretreated corn stover and switchgrass using two different methods to control contamination: either by autoclaving the pretreated feedstocks prior to enzymatic hydrolysis, or by introducing antibiotics duringmore » the hydrolysis of non-autoclaved feedstocks. We then performed extensive chemical analysis, chemical genomics, and comparative fermentations to evaluate any differences between these two different methods used for producing corn stover and switchgrass hydrolysates. Autoclaving the pretreated feedstocks could eliminate the contamination for a variety of feedstocks, whereas the antibiotic gentamicin was unable to control contamination consistently during hydrolysis. Compared to the addition of gentamicin, autoclaving of biomass before hydrolysis had a minimal effect on mineral concentrations, and showed no significant effect on the two major sugars (glucose and xylose) found in these hydrolysates. However, autoclaving elevated the concentration of some furanic and phenolic compounds. Chemical genomics analyses using Saccharomyces cerevisiae strains indicated a high correlation between the AFEX-pretreated hydrolysates produced using these two methods within the same feedstock, indicating minimal differences between the autoclaving and antibiotic methods. Comparative fermentations with S. cerevisiae and Zymomonas mobilis also showed that autoclaving the AFEX-pretreated feedstocks had no significant effects on microbial performance in these hydrolysates. In conclusion, our results showed that autoclaving the pretreated feedstocks offered advantages over the addition of antibiotics for hydrolysate production. The autoclaving method produced a more consistent quality of hydrolysate.« less

Endoplasmic reticulum stress responses function in the HRT-mediated hypersensitive response in Nicotiana benthamiana.

PubMed

Moon, Ju Yeon; Lee, Jeong Hee; Oh, Chang-Sik; Kang, Hong-Gu; Park, Jeong Mee

2016-12-01

HRT is a plant coiled-coil, nucleotide-binding and leucine-rich repeat (CC-NB-LRR) disease resistance protein that triggers the hypersensitive response (HR) on recognition of Turnip crinkle virus (TCV) coat protein (CP). The molecular mechanism and significance of HR-mediated cell death for TCV resistance have not been fully elucidated. To identify the genes involved in HRT/TCV CP-mediated HR in Nicotiana benthamiana, we performed virus-induced gene silencing (VIGS) of 459 expressed sequence tags (ESTs) of pathogen-responsive Capsicum annuum genes. VIGS of CaBLP5, which encodes an endoplasmic reticulum (ER)-associated immunoglobulin-binding protein (BiP), silenced NbBiP4 and NbBiP5 and significantly reduced HRT-mediated HR. The induction of ER stress-responsive genes and the accumulation of ER-targeted BiPs in response to HRT-mediated HR suggest that ER is involved in HR in N. benthamiana. BiP4/5 silencing significantly down-regulated HRT at the mRNA and protein levels, and affected SGT1 and HSP90 expression. Co-expression of TCV CP in BiP4/5-silenced plants completely abolished HRT induction. Transient expression of TCV CP alone induced selected ER stress-responsive gene transcripts only in Tobacco rattle virus (TRV)-infected plants, and most of these genes were induced by HRT/TCV CP, except for bZIP60, which was induced specifically in response to HRT/TCV CP. TCV CP-mediated induction of ER stress-responsive genes still occurred in BiP4/5-silenced plants, but HRT/TCV CP-mediated induction of these genes was defective. Tunicamycin, a chemical that inhibits protein N-glycosylation, inhibited HRT-mediated HR, suggesting that ER has a role in HR regulation. These results indicate that BiP and ER, which modulate pattern recognition receptors in innate immunity, also regulate R protein-mediated resistance. © 2016 BSPP and John Wiley & Sons Ltd.

Clobetasol propionate shampoo 0.05% is efficacious and safe for long-term control of scalp psoriasis.

PubMed

Poulin, Yves; Papp, Kim; Bissonnette, Robert; Guenther, Lyn; Tan, Jerry; Lynde, Charles; Kerrouche, Nabil; Villemagne, Hervé

2010-01-01

Clobetasol propionate (CP) shampoo 0.05% is an efficacious and safe treatment for scalp psoriasis. The aim of this double-blind, randomized, placebo-controlled study was to determine if CP shampoo is suitable for long-term disease control. Participants with moderate to severe scalp psoriasis (global severity score [GSS] of 3 or 4 on a scale of 0 [clear] to 5 [very severe]) first received once daily CP shampoo treatment for up to 4 weeks. Responders were subsequently randomized to receive the CP shampoo or vehicle twice weekly maintenance regimen for up to 6 months. When relapse occurred (defined as GSS > 2), participants resumed once daily CP shampoo treatment; when symptoms diminished (GSS < or = 2), they readopted the twice weekly maintenance regimen. At all visits significantly more participants treated with CP shampoo did not relapse compared with participants treated with vehicle (P < .001). Only approximately one-third of participants treated with vehicle remained relapse free at 1 month, while this rate was observed approximately 3.5 months later (4.5 months after baseline of maintenance phase) in the CP shampoo group. After 6 months 31.1% (33/106) of participants in the CP shampoo group were still relapse free versus 8.1% (9/111) of participants in the vehicle group. There was no greater incidence of skin atrophy, telangiectasia, or hypothalamic-pituitary-adrenal (HPA) axis suppression in the CP shampoo group compared with the vehicle group. Clobetasol propionate shampoo is efficacious and safe for acute management and long-term maintenance of moderate to severe scalp psoriasis.

Structures and properties of spherical 90-vertex fullerene-like nanoballs.

PubMed

Scheer, Manfred; Schindler, Andrea; Bai, Junfeng; Johnson, Brian P; Merkle, Roger; Winter, Rainer; Virovets, Alexander V; Peresypkina, Eugenia V; Blatov, Vladislav A; Sierka, Marek; Eckert, Hellmut

2010-02-15

By applying the proper stoichiometry of 1:2 to [Cp(R)Fe(eta(5)-P(5))] and CuX (X=Cl, Br) and dilution conditions in mixtures of CH(3)CN and solvents like CH(2)Cl(2), 1,2-Cl(2)C(6)H(4), toluene, and THF, nine spherical giant molecules having the simplified general formula [Cp(R)Fe(eta(5)-P(5))]@[{Cp(R)Fe(eta(5)-P(5))}(12){CuX}(25)(CH(3)CN)(10)] (Cp(R)=eta(5)-C(5)Me(5) (Cp*); eta(5)-C(5)Me(4)Et (Cp(Et)); X=Cl, Br) have been synthesized and structurally characterized. The products consist of 90-vertex frameworks consisting of non-carbon atoms and forming fullerene-like structural motifs. Besides the mostly neutral products, some charged derivatives have been isolated. These spherical giant molecules show an outer diameter of 2.24 (X=Cl) to 2.26 nm (X=Br) and have inner cavities of 1.28 (X=Cl) and 1.20 nm (X=Br) in size. In most instances the inner voids of these nanoballs encapsulate one molecule of [Cp*Fe(eta(5)-P(5))], which reveals preferred orientations of pi-pi stacking between the cyclo-P(5) rings of the guest and those of the host molecules. Moreover, pi-pi and sigma-pi interactions are also found in the packing motifs of the balls in the crystal lattice. Electrochemical investigations of these soluble molecules reveal one irreversible multi-electron oxidation at E(p)=0.615 V and two reduction steps (-1.10 and -2.0 V), the first of which corresponds to about 12 electrons. Density functional calculations reveal that during oxidation and reduction the electrons are withdrawn or added to the surface of the spherical nanomolecules, and no Cu(2+) species are involved.

Gas-phase ionization energetics, electron-transfer kinetics, and ion solvation thermochemistry of decamethylmetallocenes, chromocene, and cobaltocene

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ryan, M.F.; Richardson, D.E.; Lichtenberger, D.L.

1994-04-01

The gas-phase free energies of ionization, [Delta]G[sub i][degrees] for Cp*[sub 2]Mn, Cp*[sub 2]Fe, Cp*[sub 2]Ni, Cp*[sub 2]Os, Cp[sub 2]Cr, and Cp[sub 2]Co (Cp = [eta][sup 5]-cyclopentadienyl, Cp[sup *] = [eta][sup 5]-pentamethylcyclopentadienyl) have been determined by using the electron-transfer equilibrium (ETE) technique and Fourier transform ion cyclotron resonance mass spectrometry. The high-resolution valence photoelectron spectra of bis(benzene)chromium(0), Bz[sub 2]Cr, Cp*[sub 2]Os, and Cp*[sub 2]Ru have also been measured. Most of the [Delta]G[sub i][degrees] values are referenced to the estimated [Delta]G[sub i][degrees] value of Bz[sub 2]Cr, for which the narrow first ionization band at 5.473 [+-] 0.005 eV is assigned as themore » adiabatic ionization potential. The [Delta]S[sub i][degrees] for ionization of Bz[sub 2]Cr is assumed to be equal to the electronic entropy change, [Delta]S[sub elec][degrees] (=1.4 cal mol[sup [minus]1] K[sup [minus]1]), and the difference between the integrated heat capacities for Bz[sub 2]Cr and Bz[sub 2]Cr[sup +] is also assumed to be negligible near room temperature [Delta]H[sub i,0][degrees] [approx] [Delta]H[sub i,350][degrees], leading to [Delta]G[sub i][degrees] (Bz[sub 2]-Cr) = 125.6 [+-] 1.0 kcal mol[sup [minus]1]. Through the use of thermochemical cycles, estimates are given for the average heterolytic and homolytic M-Cp bond disruption enthalpies of Cp[sub 2]Cr[sup +/0] and Cp[sub 2]Co[sup +/0]. 46 refs., 7 figs., 4 tabs.« less

Proton Order-Disorder Phenomena in a Hydrogen-Bonded Rhodium-η(5)-Semiquinone Complex: A Possible Dielectric Response Mechanism.

PubMed

Mitsumi, Minoru; Ezaki, Kazunari; Komatsu, Yuuki; Toriumi, Koshiro; Miyatou, Tatsuya; Mizuno, Motohiro; Azuma, Nobuaki; Miyazaki, Yuji; Nakano, Motohiro; Kitagawa, Yasutaka; Hanashima, Takayasu; Kiyanagi, Ryoji; Ohhara, Takashi; Nakasuji, Kazuhiro

2015-06-26

A newly synthesized one-dimensional (1D) hydrogen-bonded (H-bonded) rhodium(II)-η(5)-semiquinone complex, [Cp*Rh(η(5)-p-HSQ-Me4)]PF6 ([1]PF6; Cp* = 1,2,3,4,5-pentamethylcyclopentadienyl; HSQ = semiquinone) exhibits a paraelectric-antiferroelectric second-order phase transition at 237.1 K. Neutron and X-ray crystal structure analyses reveal that the H-bonded proton is disordered over two sites in the room-temperature (RT) phase. The phase transition would arise from this proton disorder together with rotation or libration of the Cp* ring and PF6(-) ion. The relative permittivity εb' along the H-bonded chains reaches relatively high values (ca., 130) in the RT phase. The temperature dependence of (13)C CP/MAS NMR spectra demonstrates that the proton is dynamically disordered in the RT phase and that the proton exchange has already occurred in the low-temperature (LT) phase. Rate constants for the proton exchange are estimated to be 10(-4)-10(-6) s in the temperature range of 240-270 K. DFT calculations predict that the protonation/deprotonation of [1](+) leads to interesting hapticity changes of the semiquinone ligand accompanied by reduction/oxidation by the π-bonded rhodium fragment, producing the stable η(6)-hydroquinone complex, [Cp*Rh(3+)(η(6)-p-H2Q-Me4)](2+) ([2](2+)), and η(4)-benzoquinone complex, [Cp*Rh(+)(η(4)-p-BQ-Me4)] ([3]), respectively. Possible mechanisms leading to the dielectric response are discussed on the basis of the migration of the protonic solitons comprising of [2](2+) and [3], which would be generated in the H-bonded chain. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The two types of ENSO in CMIP5 models

NASA Astrophysics Data System (ADS)

Kim, Seon Tae; Yu, Jin-Yi

2012-06-01

In this study, we evaluate the intensity of the Central-Pacific (CP) and Eastern-Pacific (EP) types of El Niño-Southern Oscillation (ENSO) simulated in the pre-industrial, historical, and the Representative Concentration Pathways (RCP) 4.5 experiments of the Coupled Model Intercomparison Project Phase 5 (CMIP5). Compared to the CMIP3 models, the pre-industrial simulations of the CMIP5 models are found to (1) better simulate the observed spatial patterns of the two types of ENSO and (2) have a significantly smaller inter-model diversity in ENSO intensities. The decrease in the CMIP5 model discrepancies is particularly obvious in the simulation of the EP ENSO intensity, although it is still more difficult for the models to reproduce the observed EP ENSO intensity than the observed CP ENSO intensity. Ensemble means of the CMIP5 models indicate that the intensity of the CP ENSO increases steadily from the pre-industrial to the historical and the RCP4.5 simulations, but the intensity of the EP ENSO increases from the pre-industrial to the historical simulations and then decreases in the RCP4.5 projections. The CP-to-EP ENSO intensity ratio, as a result, is almost the same in the pre-industrial and historical simulations but increases in the RCP4.5 simulation.

The PedsQL in pediatric cerebral palsy: reliability and validity of the Chinese version pediatric quality of life inventory 4.0 generic core scales and 3.0 cerebral palsy module.

PubMed

Yang, Xue; Xiao, Nong; Yan, Jianying

2011-03-01

This investigation examines the reliability, validity, and sensitivity of the Chinese version Pediatric Quality of Life Inventory (PedsQL) 4.0 Generic Core Scales and 3.0 cerebral palsy (CP) Module in pediatric CP. The study sample was comprised of 126 parents of children with CP between the ages of 2 and 12 years including 18 child respondents 5-12 years of age. Mean age of the 87 boys (69.0%) and 39 girls (31.0%) was 4 years 1 month (SD 2 years 2 month). Reliability was demonstrated for the PedsQL 4.0 (α = 0.86 child, 0.89 parent) and CP Module (α = 0.91 child, 0.96 parent). The PedsQL 4.0 distinguished between healthy children and children with CP. Construct validity of the CP Module was supported through an analysis of the intercorrelations between the Generic Core Scale scores and the CP Module Scale scores and exploratory factor analysis of PedsQL items. The findings provide support for the measurement properties of the Chinese version PedsQL 4.0 Generic Core Scales and 3.0 CP Module in pediatric CP.

Depopulation of highly excited singlet states of DNA model compounds: quantum yields of 193 and 245 nm photoproducts of pyrimidine monomers and dinucleoside monophosphates.

PubMed

Gurzadyan, G G; Görner, H

1996-02-01

Formation of uracil and orotic acid photodimers, uridine and 5'-UMP photohydrates, TpT photodimers and (6-4)photoproducts, dCpT photohydrates and (6-4)photoproducts and UpU, CpC and CpU photohydrates were studied in neutral deoxygenated aqueous solution at room temperature upon irradiation at either 193 or 254 nm. The photoproducts were identified and quantified and the contribution from photoionization to substrate decomposition, using lambda irr = 193 nm, was separated. The ratio of the quantum yields of respective stable products, eta = phi 193/phi 254, is indicative of the yield of internal conversion from the second to the first excited singlet state, S2-->S1. For the observed photodimers eta decreases from 0.94 for uracil to 0.7 for TpT and further to 0.55 for orotic acid. For the (6-4)photoproducts of TpT and dCpT eta = 0.5-0.8 and for the photohydrates in the cases of UpU, CpC, CpU and dCpT eta ranges from 0.55 to 1.

Isolation and Molecular Characterization of Novel Chlorpyrifos and 3,5,6-trichloro-2-pyridinol-degrading Bacteria from Sugarcane Farm Soils

PubMed Central

Rayu, Smriti; Nielsen, Uffe N.; Nazaries, Loïc; Singh, Brajesh K.

2017-01-01

Chlorpyrifos (CP) is one of the most widely used organophosphate pesticides in agriculture worldwide, but its extensive use has led to the contamination of various soil and water systems. Microbial bioremediation is considered to be one of the most viable options for the removal of CP from the environment; however, little is known about the soil bacterial diversity that degrade CP. Sequential soil and liquid culture enrichments enabled the isolation of bacterial CP degraders with sequence homologies to Xanthomonas sp., Pseudomonas sp., and Rhizobium sp. The efficacy of the three isolated strains: Xanthomonas sp. 4R3-M1, Pseudomonas sp. 4H1-M3, and Rhizobium sp. 4H1-M1 was further investigated for biodegradation of CP and its primary metabolic product, 3,5,6-trichloro-2-pyridinol (TCP). The results indicate that all three bacterial strains almost completely metabolized CP (10 mg/L) and TCP, occurring as a metabolic degradation product, in mineral salt media as a sole source of carbon and nitrogen. The isolated bacterial strains Xanthomonas sp. 4R3-M1 and Pseudomonas sp. 4H1-M3 could also degrade TCP (10 mg/L) as a sole carbon and nitrogen source, when provided externally. Thus, these bacterial strains may be effective in practical application of bioremediation of both CP and TCP. PMID:28421040

A Nano-sized Supramolecule Beyond the Fullerene Topology**

PubMed Central

Dielmann, Fabian; Heindl, Claudia; Hastreiter, Florian; Peresypkina, Eugenia V; Virovets, Alexander V; Gschwind, Ruth M; Scheer, Manfred

2014-01-01

The reaction of [CpBnFe(η5-P5)] (1) (CpBn=η5-C5(CH2Ph)5) with CuI selectively yields a novel spherical supramolecule (CH2Cl2)3.4@[(CpBnFeP5)12{CuI}54(MeCN)1.46] (2) showing a linkage of the scaffold atoms which is beyond the Fullerene topology. Its extended CuI framework reveals an outer diameter of 3.7 nm—a size that has not been reached before using five-fold symmetric building blocks. Furthermore, 2 shows a remarkable solubility in CH2Cl2, and NMR spectroscopy reveals that the scaffold of the supramolecule remains intact in solution. In addition, a novel 2D polymer [{CpBnFe(η5-P5)}2{Cu6(μ-I)2(μ3-I)4}]n (3) with an uncommon structural motif was isolated. Its formation can be avoided by using a large excess of CuI in the reaction with 1. PMID:25288480

Methylation analysis of p16, SLIT2, SCARA5, and Runx3 genes in hepatocellular carcinoma

PubMed Central

Sun, Gaofeng; Zhang, Chen; Feng, Min; Liu, Wensheng; Xie, Huifang; Qin, Qin; Zhao, E.; Wan, Li

2017-01-01

Abstract This study is to investigate the methylation status of multiple tumor suppressor 1 (p16), secreted glycoprotein 2 (SLIT2), scavenger receptor class A, member 5 putative (SCARA5), and human runt-related transcription factor 3 (Runx3) genes in the peripheral blood of hepatocellular carcinoma (HCC). This is a case–control study. The peripheral blood samples were collected from 25 HCC patients, 25 patients with high risk of HCC (defined as “internal control group”), and 25 healthy individuals (defined as “external control group”), respectively. Then the methylation status of p16, SLIT2, SCARA5, and Runx3 genes in the blood samples were analyzed by pyrosequencing. The relationship between the methylation and the clinical features of HCC patients were evaluated. The methylation levels in the 7 CpG loci of p16 gene in HCC patients were low and without statistically significant difference (P > .05) compared to the control groups. Although the methylation levels of CpG3 and CpG4 in SLIT2 gene loci were higher than those of the control groups, there was no statistically significant difference (P > .05). However, the methylation rate of CpG2 locus in SCARA5 gene in HCC patients was significantly higher (P < .05). And the methylation rates of CpG1, CpG2, CpG3, CpG4, CpG5, and CpG8 in Runx3 gene in HCC patients were significantly different to that of control groups (P < .05). We also have analyzed the correlations between the CpG islands methylation of Runx3 or SCARA5 genes and the age, gender, hepatitis B, liver cirrhosis, alpha fetal protein, or hepatitis B surface antigen (HBsAg) of the HCC patients, which all showed no significant correlations (P > .05). The methylation status of SCARA5 and Runx3 genes are abnormal in HCC patients, which may further be used as molecular markers for early auxiliary diagnosis of liver cancer. PMID:29019900

Accessing Valuable Ligand Supports for Transition Metals: A Modified, Intermediate Scale Preparation of 1,2,3,4,5-Pentamethylcyclopentadiene.

PubMed

Call, Zachary; Suchewski, Meagan; Bradley, Christopher A

2017-03-20

A reliable, intermediate scale preparation of 1,2,3,4,5-pentamethylcyclopentadiene (Cp*H) is presented, based on modifications of existing protocols that derive from initial 2-bromo-2-butene lithiation followed by acid mediated dienol cyclization. The revised synthesis and purification of the ligand avoids the use of mechanical stirring while still permitting access to significant quantities (39 g) of Cp*H in good yield (58%). The procedure offers other additional benefits, including a more controlled quench of excess lithium during the production of the intermediate heptadienols and a simplified isolation of Cp*H of sufficient purity for metallation with transition metals. The ligand was subsequently used to synthesize [Cp*MCl2]2 complexes of both iridium and ruthenium to demonstrate the utility of the Cp*H prepared and purified by our method. The procedure outlined herein affords substantial quantities of a ubiquitous ancillary ligand support used in organometallic chemistry while minimizing the need for specialized laboratory equipment, thus providing a simpler and more accessible entry point into the chemistry of 1,2,3,4,5-pentamethylcyclopentadiene.

Synthesis of Ruthenium Carbonyl Complexes with Phosphine or Substituted Cp Ligands, and Their Activity in the Catalytic Deoxygenation of 1,2-Propanediol

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ghosh, Prasenjit; Fagan, Paul J.; Marshall, William J.

2009-07-20

A ruthenium hydride with a bulky substituted Cp ligand, (CpiPr4)Ru(CO)2H (CpiPr4 = C5(i-C3H7)4H) was prepared from the reaction of Ru3(CO)12 with 1,2,3,4-tetraisopropylcyclopentadiene. The molecular structure of (CpiPr4)Ru(CO)2H was determined by x-ray crystallography. The ruthenium hydride complex (C5Bz5)Ru(CO)2H (Bz = CH2Ph) was similarly prepared. The Ru-Ru bonded dimer, [(1,2,3-trimethylindenyl)Ru(CO)2]2, was produced from the reaction of 1,2,3-trimethylindene with Ru3(CO)12, and protonation of this dimer with HOTf gives {[(1,2,3-trimethylindenyl)Ru(CO)2]2(μ H)}+OTf –. A series of ruthenium hydride complexes CpRu(CO)(L)H [L = P(OPh)3, PCy3, PMe3, P(p C6H4F)3] were prepared by reaction of Cp(CO)2RuH with added L. Protonation of (CpiPr4)Ru(CO)2H, Cp*Ru(CO)2H or CpRu(CO)[P(OPh)3]H by HOTf 80more » °C led to equilibria with the cationic dihydrogen complexes, but H2 was released at higher temperatures. Protonation of CpRu[P(OPh)3]2H with HOTf gave an observable dihydrogen complex, {CpRu[P(OPh)3]2(η2 H2)}+OTf – that was converted at -20 °C to the dihydride complex {CpRu[P(OPh)3]2(H)2}+OTf –. These Ru complexes serve as catalyst precursors for the catalytic deoxygenation of 1,2-propanediol to give n-propanol. The catalytic reactions were carried out in sulfolane solvent with added HOTf under H2 (750 psi) at 110 °C. This work was supported by the U.S. Department of Energy's (DOE) Office of Basic Energy Sciences, Chemical Sciences program. Pacific Northwest National Laboratory is operated by Battelle for DOE.« less

Exceptional sensitivity of metal-aryl bond energies to ortho-fluorine substituents: influence of the metal, the coordination sphere, and the spectator ligands on M-C/H-C bond energy correlations.

PubMed

Clot, Eric; Mégret, Claire; Eisenstein, Odile; Perutz, Robin N

2009-06-10

DFT calculations are reported of the energetics of C-H oxidative addition of benzene and fluorinated benzenes, Ar(F)H (Ar(F) = C(6)F(n)H(5-n), n = 0-5) at ZrCp(2) (Cp = eta(5)-C(5)H(5)), TaCp(2)H, TaCp(2)Cl, WCp(2), ReCp(CO)(2), ReCp(CO)(PH(3)), ReCp(PH(3))(2), RhCp(PH(3)), RhCp(CO), IrCp(PH(3)), IrCp(CO), Ni(H(2)PCH(2)CH(2)PH(2)), Pt(H(2)PCH(2)CH(2)PH(2)). The change in M-C bond energy of the products fits a linear function of the number of fluorine substituents, with different coefficients corresponding to ortho-, meta-, and para-fluorine. The values of the ortho-coefficient range from 20 to 32 kJ mol(-1), greatly exceeding the values for the meta- and para-coefficients (2.0-4.5 kJ mol(-1)). Similarly, the H-C bond energies of Ar(F)H yield ortho- and para-coefficients of 10.4 and 3.4 kJ mol(-1), respectively, and a negligible meta-coefficient. These results indicate a large increase in the M-C bond energy with ortho-fluorine substitution on the aryl ring. Plots of D(M-C) vs D(H-C) yield slopes R(M-C/H-C) that vary from 1.93 to 3.05 with metal fragment, all in excess of values of 1.1-1.3 reported with other hydrocarbyl groups. Replacement of PH(3) by CO decreases R(M-C/H-C) significantly. For a given ligand set and metals in the same group of the periodic table, the value of R(M-C/H-C) does not increase with the strength of the M-C bond. Calculations of the charge on the aryl ring show that variations in ionicity of the M-C bonds correlate with variations in M-C bond energy. This strengthening of metal-aryl bonds accounts for numerous experimental results that indicate a preference for ortho-fluorine substituents.

Progression of recurrent acute and chronic pancreatitis: A short-term follow up study from a southern Indian centre.

PubMed

Kamath, M Ganesh; Pai, C Ganesh; Kamath, Asha

2016-11-01

Little data exist on the progression of recurrent acute (RAP) and chronic pancreatitis (CP) from regions from where the entity of tropical chronic pancreatitis was originally described. The study aimed to follow up patients with RAP and CP seen at a southern Indian centre for progression of disease over time. Prospectively enrolled patients with RAP and CP were followed up, and the alcoholic and idiopathic subgroups were assessed for progression of structural and functional changes in the organ. One hundred and forty patients (RAP = 44; 31.4 %, CP = 96; 68.5 %) were followed up over a median 12.2 (interquartile range 12.0-16.8) months. The cause was alcohol in 31 (22.1 %) and not evident in 109 (77.8 %). The disease progressed from RAP to CP in 7 (15.9 %), 6 (16.2 %) out of 37 in the idiopathic and 1 (14.2 %; p = 1.00) out of 7 in the alcoholic subgroups. Three (42.8 %) and 1 (14.2 %) developed steatorrhea and diabetes mellitus (DM), respectively, and 2 (4.5 %) developed calcification. Established CP progressed in 19 (19.7 %), 1 (1.0 %), 5 (5.2 %), 2 (2.0 %) and 11 (11.4 %) newly developed DM, steatorrhea, calcification and duct dilation during follow up. Among the idiopathic and alcoholic CP, disease progression was seen in 15 (20.8 %) out of 72 and 4 (16.6 %) out of 24 respectively. Idiopathic RAP and CP progressed during the short-term follow up. This is similar to other etiological forms of pancreatitis, as described from elsewhere in the world.

Transdermal permeation of WIN 55,212-2 and CP 55,940 in human skin in vitro.

PubMed

Valiveti, Satyanarayana; Kiptoo, Paul K; Hammell, Dana C; Stinchcomb, Audra L

2004-06-18

Synthetic cannabinoids have a promising future as treatments for nausea, appetite modulation, pain, and many neurological disorders. Transdermal delivery is a convenient and desirable dosage form for these drugs and health conditions. The aim of the present study was to investigate the in vitro transdermal permeation of two synthetic cannabinoids, WIN 55,212-2 and CP 55,940. Transdermal flux, drug content in the skin, and lag times were measured in split-thickness human abdominal skin in flow-through diffusion cells with receiver solutions of 4% bovine serum albumin (BSA) or 0.5% Brij 98. Differential thermal analysis (DSC) was performed in order to determine heats of fusion, melting points, and relative thermodynamic activities. The in vitro diffusion studies in 0.5% Brij 98 indicated that WIN 55,212-2 diffuses across human skin faster than CP 55,940. The WIN 55,212-2 skin disposition concentration levels were also significantly higher than that of CP 55,940. Correspondingly, CP 55,940 was significantly metabolized in the skin. WIN 55,212-2 flux and skin disposition were significantly lower into 4% BSA than into 0.5% Brij 98 receiver solutions. There was no significant difference in the flux, lag time, and drug content in the skin of CP 55,940 in 4% BSA versus 0.5% Brij 98 receiver solutions. The DSC studies showed that CP 55,940 had a significantly lower melting point, smaller heat of fusion, and corresponding higher calculated thermodynamic activity than the more crystalline WIN 55,212-2 mesylate salt. The permeation results indicated that WIN 55,212-2 mesylate, CP 55,940, and other potent synthetic cannabinoids with these physicochemical properties could be ideal candidates for the development of a transdermal therapeutic system. Copyright 2004 Elsevier B.V.

Incidence and risk factors for post-ERCP pancreatitis in chronic pancreatitis.

PubMed

Zhao, Zhen-Hua; Hu, Liang-Hao; Ren, Hong-Bo; Zhao, An-Jing; Qian, Yang-Yang; Sun, Xiao-Tian; Su, Song; Zhu, Shu-Guang; Yu, Jin; Zou, Wen-Bin; Guo, Xiao-Rong; Wang, Lei; Li, Zhao-Shen; Liao, Zhuan

2017-09-01

Almost all studies on post-ERCP pancreatitis (PEP) have mainly involved patients with biliary diseases rather than chronic pancreatitis (CP), and the concept that CP seems to be a protective factor associated with PEP has not been studied in detail. The aim of this study was to determine the incidence of PEP in patients with CP at different clinical stages and to identify the predictive and protective factors of PEP in a large cohort. In this observational cohort study, medical records of patients with CP (CP group) and biliary diseases (BD group) in a tertiary hospital from January 2011 to May 2015 were examined. The difference in the incidence of PEP between CP group and BD group and the risk of PEP at different clinical stages of CP were calculated by the χ 2 test or the Fisher exact test. The predictive and protective factors for PEP were investigated by univariate and multivariate analysis. In total, 2028 ERCP procedures were performed in 1301 patients with CP and 2000 procedures in 1655 patients with BD. The overall incidence of PEP in CP group (4.5%) was similar to that in the BD group (4.8%; P = .747). However, CP patients had significantly lower rates of moderate and severe attacks (0% vs 1.3%, P < .01). According to the M-ANNHEIM classification, the PEP incidences of CP at stages 0, I, II, III, and IV were 4.4%, 5.1%, 3.8%, 2.0%, and 2.0%, respectively. CP patients at stage Ia had the highest PEP incidence (8.0%) among all CP patients, significantly higher than that at stages Ib + Ic (3.9%) and II (3.8%). Female gender, history of acute pancreatitis, and prior PEP were independent risk factors of PEP, whereas extracorporeal shock wave lithotripsy was a protective factor. Compared with BD patients, CP patients had similar incidence of PEP overall but lower grades of severity. The incidence of PEP in CP patients decreased significantly with disease progression. (Clinical trial registration number: NCT02781987.). Copyright © 2017 American Society for Gastrointestinal Endoscopy. Published by Elsevier Inc. All rights reserved.

Inhibition of emesis by tachykinin NK1 receptor antagonists in Suncus murinus (house musk shrew).

PubMed

Rudd, J A; Ngan, M P; Wai, M K

1999-02-05

The anti-emetic potential of CP-122,721 ((+)-2S,3S)-3-(2-methoxy-5-trifluoromethoxybenzyl)amino-2-phenylpi peridine), CP-99,994 ((+)-(2S,3S)-3-(2-methoxybenzylamino)-2-phenylpiperidine), CP-100,263 ((-)-(2R,3R)-3-(2-methoxybenzylamino)-2-phenylpiperidine), RP 67580 ((3R, 7aR)-7,7-diphenyl-2-[1-imino-2-(2-methoxyphenyl)ethyl] po-hydroisoindol-4-one), FK 888 (N2-[(4R)-4-hydroxy-1-(1-methyl-1H-in-dole-3-yl)carbonyl-L-propyl] -N-methyl-N-phenylmethyl-1-3-(2-naphthyl)-alaninamide) and GR 82334 ([D-Pro9[spiro-g-lactam]Leu10]-physalaemin-(1-11)) was investigated to inhibit nicotine (5 mg/kg, s.c.)-, copper sulphate pentahydrate (120 mg/kg, intragastric)- and motion (4 cm horizontal displacement at 1 Hz for 5 min)-induced emesis in Suncus murinus. A 30 min intraperitoneal pre-treatment with CP-122,721, CP-99,994, RP 67580 and FK 888 significantly (P < 0.05) antagonized nicotine-induced emesis with ID50 values of 2.1, 2.3, 13.5 and 19.2 mg/kg, respectively CP-100,263, the less active enantiomer of CP-99,994, was inactive at doses up to 10 mg/kg. Infusion of GR 82334, CP-122,721, CP-99,994 and FK 888 into the dorsal vagal complex of the hindbrain also antagonized nicotine-induced emesis yielding ID50 values of 1.1, 3.0, 3.3 and 58.0 microg/dorsal vagal complex, respectively RP 67580 and CP-100,263 were inactive. RP 67580 and FK 888 failed to antagonize copper sulphate-induced emesis but CP-122,721 and CP-99,994 were active yielding ID50 values of 2.2 and 3.0 mg/kg, i.p., respectively. CP-99,994 also completely prevented motion-induced emesis at 10 mg/kg, i.p. (P < 0.05) and RP 67580 produced a significant reduction of motion-induced emesis at 10 mg/kg, i.p. (P < 0.05). These studies provide evidence of a central site of action of tachykinin NK1 receptor antagonists to inhibit nicotine-induced emesis in S. murinus and confirm the broad profile of inhibitory action. The rank order of potency of the antagonists following the intra-dorsal vagal complex administration suggests that the S. murinus tachykinin NK1 receptor has a unique pharmacological profile.

The Effect of Chronic Prostatitis/Chronic Pelvic Pain Syndrome (CP/CPPS) on Erectile Function: A Systematic Review and Meta-Analysis.

PubMed

Chen, Xiang; Zhou, ZhiRui; Qiu, XiaoChun; Wang, Bin; Dai, JiCan

2015-01-01

High prevalence of erectile dysfunction (ED) has been observed in patients with chronic prostatitis/chronic pelvic pain syndrome (CP/CPPS). However, whether or not CP/CPPS is a risk factor of ED remains unknown and controversial. Therefore, we conducted this systematic review and meta-analysis to evaluate the relationship between CP/CPPS and ED. PubMed, Embase, Web of Science, and The Cochrane Library were searched up to November 11, 2014 to identify studies reporting the association between CP/CPPS and ED. Case-control, cohort and cross-sectional studies were included. Quality of the included studies was assessed. The odds ratio of ED and the mean difference of five-item International Index of Erectile Function (IIEF-5) score were pooled using a random effects model. Subgroup analysis and sensitivity analyses were performed. Three cross-sectional studies, two case-control studies, and four retrospective studies with 31,956 participants were included to calculate the pooled odds ratio of ED, and two studies with 1499 participants were included to calculate the pooled mean difference of IIEF-5 scores. A strong correlation was found between CP/CPPS and ED (pooled odds ratio: 3.02, 95% CI: 2.18-4.17, P < 0.01), with heterogeneity across studies (I2 = 65%; P < 0.01). A significant decrease in the IIFE-5 score was observed in the CP/CPPS group (pooled mean difference: -4.54, 95% CI: -5.11--3.98; P < 0.01). Our study indicates that patients with CP/CPPS have an increased risk of suffering from ED. Assessment of erectile function is necessary for the therapy of patients with CP/CPPS. Further evidence is necessary to confirm the relationship between CP/CPPS and ED.

Thermal Chemistry of Cp*W(NO)(CH2CMe3)(H)(L) Complexes (L = Lewis Base).

PubMed

Fabulyak, Diana; Handford, Rex C; Holmes, Aaron S; Levesque, Taleah M; Wakeham, Russell J; Patrick, Brian O; Legzdins, Peter; Rosenfeld, Devon C

2017-01-03

The complexes trans-Cp*W(NO)(CH 2 CMe 3 )(H)(L) (Cp* = η 5 -C 5 Me 5 ) result from the treatment of Cp*W(NO)(CH 2 CMe 3 ) 2 in n-pentane with H 2 (∼1 atm) in the presence of a Lewis base, L. The designation of a particular geometrical isomer as cis or trans indicates the relative positions of the alkyl and hydrido ligands in the base of a four-legged piano-stool molecular structure. The thermal behavior of these complexes is markedly dependent on the nature of L. Some of them can be isolated at ambient temperatures [e.g., L = P(OMe) 3 , P(OPh) 3 , or P(OCH 2 ) 3 CMe]. Others undergo reductive elimination of CMe 4 via trans to cis isomerization to generate the 16e reactive intermediates Cp*W(NO)(L). These intermediates can intramolecularly activate a C-H bond of L to form 18e cis complexes that may convert to the thermodynamically more stable trans isomers [e.g., Cp*W(NO)(PPh 3 ) initially forms cis-Cp*W(NO)(H)(κ 2 -PPh 2 C 6 H 4 ) that upon being warmed in n-pentane at 80 °C isomerizes to trans-Cp*W(NO)(H)(κ 2 -PPh 2 C 6 H 4 )]. Alternatively, the Cp*W(NO)(L) intermediates can effect the intermolecular activation of a substrate R-H to form trans-Cp*W(NO)(R)(H)(L) complexes [e.g., L = P(OMe) 3 or P(OCH 2 ) 3 CMe; R-H = C 6 H 6 or Me 4 Si] probably via their cis isomers. These latter activations are also accompanied by the formation of some Cp*W(NO)(L) 2 disproportionation products. An added complication in the L = P(OMe) 3 system is that thermolysis of trans-Cp*W(NO)(CH 2 CMe 3 )(H)(P(OMe) 3 ) results in it undergoing an Arbuzov-like rearrangement and being converted mainly into [Cp*W(NO)(Me)(PO(OMe) 2 )] 2 , which exists as a mixture of two isomers. All new complexes have been characterized by conventional and spectroscopic methods, and the solid-state molecular structures of most of them have been established by single-crystal X-ray crystallographic analyses.

Solar photocatalytic degradation of chlorophenols mixture (4-CP and 2,4-DCP): Mechanism and kinetic modelling.

PubMed

Abeish, Abdulbasit M; Ang, Ha Ming; Znad, Hussein

2015-01-01

The solar-photocatalytic degradation mechanisms and kinetics of 4-chlorophenol (4-CP) and 2,4-dichlorophenol (2,4-DCP) using TiO2 have been investigated both individually and combined. The individual solar-photocatalytic degradation of both phenolic compounds showed that the reaction rates follow pseudo-first-order reaction. During the individual photocatalytic degradation of both 4-CP and 2,4-DCP under the same condition of TiO2 (0.5 g L(-1)) and light intensities (1000 mW cm(-2)) different intermediates were detected, three compounds associated with 4-CP (hydroquinone (HQ), phenol (Ph) and 4-chlorocatechol (4-cCat)) and two compounds associated with 2,4-DCP (4-CP and Ph). The photocatalytic degradation of the combined mixture (4-CP and 2,4-DCP) was also investigated at the same conditions and different 2,4-DCP initial concentrations. The results showed that the degradation rate of 4-CP decreases when the 2,4-DCP concentration increases. Furthermore, the intermediates detected were similar to that found in the individual degradation but with high Ph concentration. Therefore, a possible reaction mechanism for degradation of this combined mixture was proposed. Moreover, a modified Langmuir-Hinshelwood (L-H) kinetic model considering all detected intermediates was developed. A good agreement between experimental and estimated results was achieved. This model can be useful for scaling-up purposes more accurately as its considering the intermediates formed, which has a significant effect on degrading the main pollutants (4-CP and 2,4-DCP).

Profiles of vocal development in Korean children with and without cleft palate.

PubMed

Ha, Seunghee

2018-01-01

This study longitudinally investigated vocal development in Korean children from 9 to 18 months of age with and without cleft palate (CP). Utterance samples were collected from 24 children with and without CP at 9, 12, 15 and 18 months of age. Each utterance was categorised into levels of vocalisation using the Korean-translated version of the Stark Assessment of Early Vocal Development-Revised (SAEVD-R). The results showed children with CP produced a significantly higher rate of precanonical vocalisations (the combination of Levels 1, 2, and 3) and a lower rate of Level 4 and 5 vocalisations than children without CP. Both groups showed decreases in Levels 1 and 2 and increases in Level 5 from 9 to 18 months of age. A significant increase in the proportion of Level 4 vocalisations across age was observed only in children without CP. Young Korean children with CP showed lower proportions of advanced vocalisation levels characterised by canonical and complex syllable structures across 9 and 18 months of age compared to children without CP.

Smoking as a risk factor for complications in chronic pancreatitis.

PubMed

Luaces-Regueira, María; Iglesias-García, Julio; Lindkvist, Björn; Castiñeira-Alvariño, Margarita; Nieto-García, Laura; Lariño-Noia, José; Domínguez-Muñoz, J Enrique

2014-03-01

Several recent studies have demonstrated the association between smoking and chronic pancreatitis (CP). However, less is known about the role of smoking in the development of CP-related complications. Our aim was to investigate the impact of smoking and alcohol consumption on age of onset and complications at CP diagnosis. A cross-sectional case-case study was performed within a prospectively collected cohort of patients with CP. Alcohol consumption and smoking habits were assessed using a standardized questionnaire. Morphologic severity was defined based on endoscopic ultrasound criteria for CP and classified as mild (3-4 criteria), moderate (5-6 criteria), and severe (≥7 criteria or calcifications). Pancreatic exocrine insufficiency (PEI) was diagnosed using the C-mixed triglyceride breath test. Odds ratios (OR) with 95% confidence intervals (CI) for CP-related complications were calculated using a case-case design. A total of 241 patients were included. Smoking was associated with PEI (OR [95% CI], 2.4 [1.17-5.16]), calcifications (OR [95% CI], 2.33 [1.10-4.95]), and severe morphologic changes (OR [95% CI], 3.41 [1.31-8.85]) but not with pseudocysts or diabetes. Neither smoking nor alcohol consumption was associated with age of onset. Tobacco, but not alcohol, is associated with PEI, calcifications, and severe morphologic (≥7 criteria or calcifications) CP at diagnosis. Smoking cessation should be encouraged in patients with CP.

Clobetasol propionate shampoo 0.05% is efficacious and safe for long-term control of moderate scalp psoriasis.

PubMed

Poulin, Yves; Papp, Kim; Bissonnette, Robert; Barber, Kirk; Kerrouche, Nabil; Villemagne, Hervé

2010-05-01

We evaluated in this study the efficacy and safety of an alternate regimen using clobetasol propionate 0.05% shampoo (CP shampoo) for long-term control of scalp psoriasis. Patients with moderate scalp psoriasis (Global Severity Score [GSS] of 3 on a 0-5 scale) first received CP shampoo once daily for 4 weeks. Patients with a GSS 2) occurred, patients received the 4-week daily CP shampoo treatment. Patients who had a GSS

Degradation mechanisms of 4-chlorophenol in a novel gas-liquid hybrid discharge reactor by pulsed high voltage system with oxygen or nitrogen bubbling.

PubMed

Zhang, Yi; Zhou, Minghua; Hao, Xiaolong; Lei, Lecheng

2007-03-01

The effect of gas bubbling on the removal efficiency of 4-chlorophenol (4-CP) in aqueous solution has been investigated using a novel pulsed high voltage gas-liquid hybrid discharge reactor, which generates gas-phase discharge above the water surface simultaneously with the spark discharge directly in the liquid. The time for 100% of 4-CP degradation in the case of oxygen bubbling (7 min) was much shorter than that in the case of nitrogen bubbling (25 min) as plenty of hydrogen peroxide and ozone formed in oxygen atmosphere enhanced the removal efficiency of 4-CP. Except for the main similar intermediates (4-chlorocatechol, hydroquinone and 1,4-benzoquinone) produced in the both cases of oxygen and nitrogen bubbling, special intermediates (5-chloro-3-nitropyrocatechol, 4-chloro-2-nitrophenol, nitrate and nitrite ions) were produced in nitrogen atmosphere. The reaction pathway of 4-CP in the case of oxygen bubbling was oxygen/ozone attack on the radical hydroxylated derivatives of 4-CP. However, in the case of nitrogen bubbling, hydroxylation was the main reaction pathway with effect of N atom on degradation of 4-CP.

Degradation of 4-Chlorophenol Under Sunlight Using ZnO Nanoparticles as Catalysts

NASA Astrophysics Data System (ADS)

Rajar, Kausar; Sirajuddin; Balouch, Aamna; Bhanger, M. I.; Sherazi, Tufail H.; Kumar, Raj

2018-03-01

Herein we demonstrate a simplistic microwave assisted chemical precipitation approach regarding the synthesis of zinc oxide nanoparticles. As-prepared ZnO nanoparticles (NPs) were characterized by UV-visible spectroscopy, Fourier transform infra-red spectroscopy, atomic force microscopy and x-ray diffractometry and scrutinized as photo-catalysts for degradation of 4-chlorophenol (4-CP) under sunlight. The study substantiated that 98.5% of 4-CP was degraded within 20 min in the absence of initiator like H2O2 which reflects an outstanding prospective use for ZnO NPs as photo-catalysts. The nanocatalysts were recycled four times and still showed catalytic efficiency up to 95.5% for degradation of 4-CP in the specified 20 min.

ALBI versus Child-Pugh grading systems for liver function in patients with hepatocellular carcinoma.

PubMed

Na, Seong K; Yim, Sun Y; Suh, Sang J; Jung, Young K; Kim, Ji H; Seo, Yeon S; Yim, Hyung J; Yeon, Jong E; Byun, Kwan S; Um, Soon H

2018-04-01

The prognostic performance of the albumin-bilirubin (ALBI) grade in hepatocellular carcinoma (HCC) as an objective method of assessing liver function was investigated. Data from 2099 patients with HCC in Korea were collected and analyzed retrospectively. The discriminative performance of ALBI grade was compared with Child-Pugh (C-P) grade for different stages or treatments. The median follow up duration was 16.2 months (range: 1.0-124.9). The median survival times were 49.7 months for C-P grade A (65.8%), 12.4 months for C-P grade B (25.5%), and 4.2 months for C-P grade C (8.6%) (P < 0.001). The median survival times were 84.2 months for ALBI grade 1 (32.8%), 25.5 months for ALBI grade 2 (53.5%), and 7.7 months for ALBI grade 3 (13.7%) (P < 0.001). In early UICC stages, ALBI grade showed better discriminative performance than C-P grade. In curative treatments, ALBI grade also showed better discriminative performance than C-P grade (Harrell's C: 0.624 (C-P grade) vs 0.667 [ALBI grade]). ALBI grade provided better prognostic performance in survival analysis and better distribution of the grades than C-P grade in HCC, suggesting that ALBI grade could be a good alternative grading system for liver function in patients with HCC. © 2018 Wiley Periodicals, Inc.

Nutritive value of extruded or multi-enzyme supplemented cold-pressed soybean cake for pigs.

PubMed

Woyengo, T A; Patterson, R; Levesque, C L

2016-12-01

The objectives were to determine the standardized ileal digestibility (SID) of AA and NE value of cold-pressed soybean cake (CP-SBC), and the effect of extrusion or adding multi-enzyme to CP-SBC diet for growing pigs. Eight ileal-cannulated pigs (initial BW = 79.7 ± 3.97 kg) were fed 4 diets in a replicated 4 × 4 Latin square design to give 8 replicates per diet. Diets included a cornstarch-based diet with CP-SBC, extruded CP-SBC, and SBC plus multi-enzyme (1,200 U of xylanase, 150 U of glucanase, 500 U of cellulase, 60 U of mannanase, 700 U of invertase, 5,000 U of protease, and 12,000 U of amylase/kilogram of diet; Superzyme-CS, 0.5 g/kg); and a N-free diet. The CP-SBC was the sole source of protein in the CP-SBC-containing diets. The ratio of cornstarch to sugar and soybean oil in CP-SBC-containing diets was identical to the N-free diet to allow calculation of energy digestibility of CP-SBC by the difference method. The evaluated CP-SBC had been produced by heating the soybean seed at 105°C for 60 min followed by pressing of the heated soybean seeds at less than 42°C (barrel temperature). On a DM basis, CP-SBC and extruded CP-SBC contained 47.8 and 47.1% CP, 15.6 and 10.5% ADF, 7.23 and 8.85% ether extract, 3.11 and 3.08% Lys, and 2.25 and 3.70 trypsin inhibitor units per mg, respectively. Extrusion increased ( < 0.001) the SID of AA for the CP-SBC by an average of 12%. Also, extrusion increased ( < 0.001) the NE value of the CP-SBC from 2,743 to 2,853 kcal/kg of DM. Supplementation of CP-SBC diet with the multi-enzyme increased ( < 0.05) the SID of Arg and Pro, and tended to increase ( < 0.1) the SID of Ile and Tyr. However, the multi-enzyme supplementation did not affect the NE value of CP-SBC. In conclusion, the CP-SBC evaluated in the present study could be an alternative source of AA and energy in swine diets, and its nutritive value can be increased by extrusion following cold-pressing. The multi-enzyme used in this study improved the digestibility of some AA, but had limited effect on energy digestibility and hence NE value of the CP-SBC.

Construction of noninterpenetrating and interpenetrating Co(ii) networks with halogenated carboxylate modulated by auxiliary N-donor co-ligands: structural diversity, electrochemical and photocatalytic properties.

PubMed

Hao, Shao Yun; Hou, Suo Xia; Van Hecke, Kristof; Cui, Guang Hua

2017-02-14

Six Co(ii)-based coordination polymers (CPs) with characteristic frameworks and topologies-namely, [Co(L1)(DCTP)] n (1), [Co(L2)(DCTP)] n (2), [Co(L3)(DCTP)] n (3), {[Co 3 (L4) 3 (DCTP) 3 ·H 2 O]·H 2 O} n (4), [Co(L5) 1.5 (DCTP)] n (5) and [Co(L6)(DCTP)] n (6)-were successfully hydrothermally synthesized by employing the halogenated linear ligand 2,5-dichloroterephthalic acid (H 2 DCTP). The interpenetrated structures could be rationally modulated by auxiliary N-donor co-ligands containing 1,1'-(1,4-butanediyl)bis-1H-benzimidazole (L1), 1,4-bis(5,6-dimethylbenzimidazol-1-yl)-2-butylene (L2), 1,2-bis(2-methylbenzimidazol-1-ylmethyl)benzene (L3), 1,4-bis(2-methylbenzimidazol-1-ylmethyl)benzene (L4), 1,2-bis(5,6-dimethylbenzimidazol-1-ylmethyl)benzene (L5) and 1,4-bis(5,6-dimethylbenzimidazol-1-ylmethyl)benzene (L6). These diaphanous crystals were clearly characterized by elemental analysis, infrared (IR) spectra and X-ray powder diffraction (XRPD) as well as single-crystal X-ray diffraction analysis. With the aid of the flexible N-donor co-ligands, CP 1 occupies a non-interpenetrated 2D sheet with the point symbol {4 4 ·6 2 } sql net topology, CP 2 possesses a 3D hexagon-shaped network with the point symbol {6 6 } three-fold interpenetrated sqc6 topology, CP 3 exhibits a 2D layer with the point symbol {4 4 ·6 2 } sql net topology, CP 4 reveals an unusual 3D framework with the point symbol {4 2 ·6 3 ·8} three-fold interpenetrated sra topology, CP 5 has a 3D hexagon-shaped network with the point symbol {6 6 } two-fold interpenetrated sqc6 topology, while CP 6 displays a 3D hexagon-shaped network with the point symbol {6 6 } three-fold interpenetrated sqc6 topology. The diverse structures of CPs 1-6 illustrate that the substitute group and position of the methyl group of the bis(benzimidazole) derivatives play a significant role in the assembly of such interpenetrated frameworks. Moreover, luminescence properties and thermal behavior, as well as the electrochemical and photocatalytic properties of CPs 1-6 on the degradation of methylene blue, are also presented.

Characterization of human cytochrome P450s involved in the bioactivation of tri-ortho-cresyl phosphate (ToCP).

PubMed

Reinen, Jelle; Nematollahi, Leyla; Fidder, Alex; Vermeulen, Nico P E; Noort, Daan; Commandeur, Jan N M

2015-04-20

Tri-ortho-cresyl phosphate (ToCP) is a multipurpose organophosphorus compound that is neurotoxic and suspected to be involved in aerotoxic syndrome in humans. It has been reported that not ToCP itself but a metabolite of ToCP, namely, 2-(ortho-cresyl)-4H-1,2,3-benzodioxaphosphoran-2-one (CBDP), may be responsible for this effect as it can irreversibly bind to human butyrylcholinesterase (BuChE) and human acetylcholinesterase (AChE). The bioactivation of ToCP into CBDP involves Cytochrome P450s (P450s). However, the individual human P450s responsible for this bioactivation have not been identified yet. In the present study, we aimed to investigate the metabolism of ToCP by different P450s and to determine the inhibitory effect of the in vitro generated ToCP-metabolites on human BuChE and AChE. Human liver microsomes, rat liver microsomes, and recombinant human P450s were used for that purpose. The recombinant P450s 2B6, 2C18, 2D6, 3A4 and 3A5 showed highest activity of ToCP-bioactivation to BuChE-inhibitory metabolites. Inhibition experiments using pooled human liver microsomes indicated that P450 3A4 and 3A5 were mainly involved in human hepatic bioactivation of ToCP. In addition, these experiments indicated a minor role for P450 1A2. Formation of CBDP by in-house expressed recombinant human P450s 1A2 and 3A4 was proven by both LC-MS and GC-MS analysis. When ToCP was incubated with P450 1A2 and 3A4 in the presence of human BuChE, CBDP-BuChE-adducts were detected by LC-MS/MS which were not present in the corresponding control incubations. These results confirmed the role of human P450s 1A2 and 3A4 in ToCP metabolism and demonstrated that CBDP is the metabolite responsible for the BuChE inactivation. Interindividual differences at the level of P450 1A2 and 3A4 might play an important role in the susceptibility of humans in developing neurotoxic effects, such as aerotoxic syndrome, after exposure to ToCP.

Glucagon-like peptide-1 reduces contractile function and fails to boost glucose utilization in normal hearts in the presence of fatty acids.

PubMed

Nguyen, T Dung; Shingu, Yasushige; Amorim, Paulo A; Schwarzer, Michael; Doenst, Torsten

2013-10-09

GLP-1 and exendin-4, which are used as insulin sensitizers or weight reducing drugs, were shown to improve glucose uptake in the heart. However, the direct effects of GLP-1 or exendin-4 on normal hearts in the presence of fatty acids, the main cardiac substrates, have never been investigated. We therefore assessed the effects of GLP-1 or exendin-4 on myocardial glucose uptake (GU), glucose oxidation (GO) and cardiac performance (CP) under conditions of fatty acid utilization. Rat hearts were perfused with only glucose (5 mM) or glucose (5 mM) plus oleate (0.4 mM) as substrates for 60 min. After 30 min, GLP-1 or exendin-4 (0.5 nM or 5 nM) was added. In the absence of oleate, GLP-1 increased both GU and GO. Exendin-4 increased GO but showed no effect on GU. Neither GLP-1 nor exendin-4 affected CP. However, when oleate was present, GLP-1 failed to stimulate glucose utilization and exendin-4 even decreased GU. Furthermore, now GLP-1 reduced CP. In contrast to prior reports, this negative inotropic effect could not be blocked by the protein kinase A inhibitor H-89. We then measured myocardial GO and CP in rats receiving a 4-week GLP-1 infusion. Interestingly, this chronic treatment resulted in a significant reduction in both GO and CP. Under the influence of oleate, GLP-1 reduces contractile function and fails to stimulate glucose utilization in normal hearts. Exendin-4 may acutely reduce cardiac glucose uptake but not contractility. We suggest advanced investigation of heart function and metabolism in patients treating with these peptides. © 2013.

Chymotrypsinogen C Genetic Variants, Including c.180TT, Are Strongly Associated With Chronic Pancreatitis in Pediatric Patients.

PubMed

Grabarczyk, Alicja Monika; Oracz, Grzegorz; Wertheim-Tysarowska, Katarzyna; Kujko, Aleksandra Anna; Wejnarska, Karolina; Kolodziejczyk, Elwira; Bal, Jerzy; Koziel, Dorota; Kowalik, Artur; Gluszek, Stanislaw; Rygiel, Agnieszka Magdalena

2017-12-01

Genetic studies in adults/adolescent patients with chronic pancreatitis (CP) identified chymotrypsinogen C (CTRC) genetic variants but their association with CP risk has been difficult to replicate. To evaluate the risk of CP associated with CTRC variants in CP pediatric patients-control study. The distribution of CTRC variants in CP pediatric cohort (n = 136, median age at CP onset 8 years) with no history of alcohol/smoking abuse was compared with controls (n = 401, median age 45). We showed that p.Arg254Trp (4.6%) and p.Lys247_Arg254del (5.3%) heterozygous mutations are frequent and significantly associated with CP risk in pediatric patients (odds ratio [OR] = 19.1; 95% CI 2.8-160; P = 0.001 and OR = 5.5; 95% CI 1.6-19.4; P = 0.001, respectively). For the first time, we demonstrated that the c.180TT genotype of common p.Gly60Gly variant is strong, an independent CP risk factor (OR = 23; 95% CI 7.7-70; P < 0.001) with effect size comparable to p.Arg254Trp mutation. The other novel observation is that common c.493+51C>A variant, both CA and AA genotype, is significantly underrepresented in CP compared with controls (15% vs 35%; OR = 0.33; 95% CI 0.19-0.59; P < 0.001 and 2.8% vs 11%; OR = 0.24; 95% CI 0.06-0.85; P = 0.027, respectively). Our study provides evidence that CTRC variants, including c.180TT (p.Gly60Gly) are strong CP risk factors. The c.493+51C>A variant may play a protective role against CP development.

Ab initio metadynamics simulations of oxygen/ligand interactions in organoaluminum clusters

DOE Office of Scientific and Technical Information (OSTI.GOV)

Alnemrat, Sufian; Hooper, Joseph P., E-mail: jphooper@nps.edu

2014-10-14

Car-Parrinello molecular dynamics combined with a metadynamics algorithm is used to study the initial interaction of O{sub 2} with the low-valence organoaluminum clusters Al{sub 4}Cp{sub 4} (Cp=C{sub 5}H{sub 5}) and Al{sub 4}Cp{sub 4}{sup *} (Cp{sup *}=C{sub 5}[CH{sub 3}]{sub 5}). Prior to reaction with the aluminum core, simulations suggest that the oxygen undergoes a hindered crossing of the steric barrier presented by the outer ligand monolayer. A combination of two collective variables based on aluminum/oxygen distance and lateral oxygen displacement was found to produce distinct reactant, product, and transition states for this process. In the methylated cluster with Cp{sup *} ligands,more » a broad transition state of 45 kJ/mol was observed due to direct steric interactions with the ligand groups and considerable oxygen reorientation. In the non-methylated cluster the ligands distort away from the oxidizer, resulting in a barrier of roughly 34 kJ/mol with minimal O{sub 2} reorientation. A study of the oxygen/cluster system fixed in a triplet multiplicity suggests that the spin state does not affect the initial steric interaction with the ligands. The metadynamics approach appears to be a promising means of analyzing the initial steps of such oxidation reactions for ligand-protected clusters.« less

Physical and Mental Quality of Life (QOL) in Chronic Pancreatitis(CP): A Case-Control Study from the NAPS2 cohort

PubMed Central

Amann, Stephen T.; Yadav, Dhiraj; Barmada, M. Micheal; O’Connell, Michael; Kennard, Elizabeth D.; Anderson, Michelle; Baillie, John; Sherman, Stuart; Romagnuolo, Joseph; Hawes, Robert H.; AlKaade, Samer; Brand, Randall E.; Lewis, Michele D.; Gardner, Timothy B.; Gelrud, Andres; Money, Mary E.; Banks, Peter A.; Slivka, Adam; Whitcomb, David C

2012-01-01

Objectives Define the Quality of Life (QOL) in chronic pancreatitis (CP) subjects Methods We studied 443 well phenotyped CP subjects and 611 controls prospectively enrolled from 20 US centers between 2000–2006 in the North American Pancreatitis Study 2 (NAPS2). Responses to the SF-12 questionnaire were used to calculate the Mental (MCS) and Physical component summary scores (PCS) with norm based scoring (normal ≥50). QOL in CP subjects was compared with controls after controlling for demographic factors, drinking history, smoking and medical conditions. QOL in CP was also compared with known scores for several chronic conditions. Results Both PCS (38±11.5 vs. 52±9.4) and MCS (44±11.5 vs. 51±9.2) were significantly lower in CP compared with controls (p<0.001). On multivariable analyses, compared to controls, a profound decrease in physical QOL (PCS 12.02 points lower) and a clinically significant decrease in mental QOL (MCS 4.24 points lower) was seen due to CP. QOL in CP was similar to (heart, kidney, liver, lung disease) or worse than (non-skin cancers, diabetes mellitus, hypertension, rheumatoid arthritis) other chronic conditions. Conclusions The impact of CP on QOL appears substantial. The QOL in CP subjects appears to be worse or similar to the QOL of many other chronic conditions. PMID:23357924

Dopamine receptor D4 promoter hypermethylation increases the risk of drug addiction.

PubMed

Ji, Huihui; Xu, Xuting; Liu, Guili; Liu, Huifen; Wang, Qinwen; Shen, Wenwen; Li, Longhui; Xie, Xiaohu; Hu, Haochang; Xu, Lei; Zhou, Wenhua; Duan, Shiwei

2018-02-01

Heroin and methylamphetamine (METH) are two addictive drugs that cause serious problems for society. Dopamine receptor D4 (DRD4), a key receptor in the dopaminergic system, may facilitate the development of drug addiction. The aim of the present study was to investigate the association between the promoter methylation level of DRD4 gene and drug addiction. Bisulfite pyrosequencing technology was used to measure the methylation levels of DRD4 promoter in 60 drug addicts and 52 matched controls. Significantly higher levels of DRD4 CpG1 and CpG4 methylation were detected in METH and heroin drug addicts compared with controls (P<0.05). Male METH addicts exhibited significantly higher DRD4 CpG1, CpG2 and CpG4 methylation levels compared with sex-matched controls (P<0.05). In heroin addicts, a positive correlation was observed between depression-dejection and DRD4 CpG5 methylation (r=0.537, P=0.039) whereas there was a negative correlation between drug usage frequency and CpG1 methylation (r=-0.632, P=0.011). In METH addicts, methylation levels were not significantly associated with depression-dejection and drug usage frequency. In addition, luciferase assays demonstrated that the target sequence of the DRD4 promoter upregulates gene expression. The results of the present study suggest that DNA methylation of DRD4 may be responsible for the pathophysiology of drug addiction.

Effect of dietary level of protein and fiber on the productive performance and health status of piglets.

PubMed

Hermes, R G; Molist, F; Ywazaki, M; Nofrarías, M; Gomez de Segura, A; Gasa, J; Pérez, J F

2009-11-01

To study the interaction between the levels of protein and fiber on the productive performance and health status of piglets, ninety-six 35-d-old piglets (9.11 +/- 0.60 kg of BW) were placed in 32 pens of 3 animals each and allotted to 4 dietary treatments for 21 d. The 4 diets were based on rice, dairy products, and soybean meal in a 2 x 2 factorial arrangement of treatments, with 2 levels of CP (15.4 vs. 19.4%, as-fed basis) and 2 levels of dietary fiber [DF; low fiber (LF) 5.3% NDF and high fiber (HF) 7.15% NDF, as-fed basis]. The HF diet was developed by supplementing the basal diet with 40 g/kg of wheat bran and 20 g/kg of sugar beet pulp. Animal performance was obtained weekly with samples of feces collected for microbiology on the first and the last experimental day and scored from 1 (liquid) to 4 (hard). On the last day, 1 pig from each pen was sampled for blood analyses of the acute-phase protein, major acute-phase protein of pigs (PigMap) and subsequently killed to register the digestive tract weight (including contents) and colon histology. Pigs fed the HF diets had greater ADG (390 vs. 457 g; P < or = 0.001) and large intestine weight (4.4 vs. 5.4% of BW; P < or = 0.05). This coincided with a greater (P < or = 0.05) short-chain fatty acid concentration (especially of acetic and butyric acids), a decrease in Escherichia coli counts (7.77 vs. 6.86 log of cfu/g of feces, P < or = 0.05), and an increase in the ratio of lactobacilli:enterobacteria (0.76 vs. 1.37, P < or = 0.05). However, CP level did not modify the productive performance, but 20% CP increased P < or = 0.05) the relative weight (% of BW) of the small (6.5 vs. 7.7) and large intestine (3.8 vs. 4.3). In the large bowel, the 20% CP diet increased the numbers of goblet cells (4.6 vs. 5.4/100 microm; P < or = 0.05) and reduced the numbers of intraepithelial lymphocytes (1.8 vs. 1.3/100 microm; P < or = 0.05). In relation to health status, increasing DF was dependent of the dietary CP content. Supplementing the 16% CP diet with DF reduced the fecal score and increased the antibiotics interventions, whereas the opposite was the case in the 20% CP diet. Pigs fed the 20% CP diet showed decreased (P < or = 0.05) PigMap concentrations than pigs fed 16% CP diets. As a whole, CP showed major effects on the gastrointestinal weight and gut barrier integrity, whereas DF increased the productive performance and promoted major changes in the microbial colonization and fermentation variables.

Search for CP Violation in Charged-Ξ and Λ Hyperon Decays

NASA Astrophysics Data System (ADS)

Holmstrom, T.; Leros, N.; Burnstein, R. A.; Chakravorty, A.; Chan, A.; Chen, Y. C.; Choong, W. S.; Clark, K.; Dukes, E. C.; Durandet, C.; Felix, J.; Fu, Y.; Gidal, G.; Gu, P.; Gustafson, H. R.; Ho, C.; Huang, M.; James, C.; Jenkins, C. M.; Jones, T.; Kaplan, D. M.; Lederman, L. M.; Longo, M. J.; Lopez, F.; Lu, L. C.; Luebke, W.; Luk, K. B.; Nelson, K. S.; Park, H. K.; Perroud, J.-P.; Rajaram, D.; Rubin, H. A.; Teng, P. K.; Volk, J.; White, C. G.; White, S. L.; Zyla, P.

2004-12-01

We have compared the p and p¯ angular distributions in 117×106 Ξ-→Λπ-→pπ-π- and 41×106 Ξ¯+→Λ¯π+→p¯π+π+ decays using a subset of the data from the HyperCP experiment (E871) at Fermilab. We find no evidence of CP violation, with the direct-CP-violating parameter AΞΛ≡(αΞαΛ-α¯Ξα¯Λ)/(αΞαΛ+α¯Ξα¯Λ)=[0.0±5.1(stat)±4.4(syst)]×10-4.

Validation of Accelerometer Cut-Points in Children With Cerebral Palsy Aged 4 to 5 Years.

PubMed

Keawutan, Piyapa; Bell, Kristie L; Oftedal, Stina; Davies, Peter S W; Boyd, Roslyn N

2016-01-01

To derive and validate triaxial accelerometer cut-points in children with cerebral palsy (CP) and compare these with previously established cut-points in children with typical development. Eighty-four children with CP aged 4 to 5 years wore the ActiGraph during a play-based gross motor function measure assessment that was video-taped for direct observation. Receiver operating characteristic and Bland-Altman plots were used for analyses. The ActiGraph had good classification accuracy in Gross Motor Function Classification System (GMFCS) levels III and V and fair classification accuracy in GMFCS levels I, II, and IV. These results support the use of the previously established cut-points for sedentary time of 820 counts per minute in children with CP aged 4 to 5 years across all functional abilities. The cut-point provides an objective measure of sedentary and active time in children with CP. The cut-point is applicable to group data but not for individual children.

Structural and Computational Studies of Cp(CO)2(PCy3)MoFBF3, a Complex with a Bound BF4- Ligand

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cheng, Tan-Yun; Szalda, David J.; Franz, James A.

2010-02-15

Hydride transfer from Cp(CO)2(PCy3)MoH to Ph3C+BF4 gives Cp(CO)2(PCy3)MoFBF3, and the crystal structure of this complex was determined. In the weakly bound FBF3 ligand, the B-F(bridging) bond length is 1.475(8) Å, which is 0.15 Å longer than the average length of the three B-F(terminal) bonds. The PCy3 and FBF3 ligands are cis to each other in the four-legged piano stool structure. Electronic structure (DFT) calculations predict the trans isomer of Cp(CO)2(PCy3)MoFBF3 to be 9.5 kcal/mol (in ΔGog,298)) less stable than the cis isomer that was crystallographically characterized. Hydride transfer from Cp(CO)2(PCy3)MoH to Ph3C+BAr'4 [Ar' = 3,5-bis(trifluoromethyl)phenyl] in CH2Cl2 solvent produces [Cp(CO)2(PCy3)Mo(ClCH2Cl)]+[BAr'4]more » , in which CH2Cl2 is coordinated to the metal. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy.« less

Nonthermal inactivation of norovirus surrogates on blueberries using atmospheric cold plasma.

PubMed

Lacombe, Alison; Niemira, Brendan A; Gurtler, Joshua B; Sites, Joseph; Boyd, Glenn; Kingsley, David H; Li, Xinhui; Chen, Haiqiang

2017-05-01

Viruses are currently the leading cause of foodborne outbreaks, most of which are associated with foods consumed raw. Cold plasma (CP) is an emerging novel nonthermal technology that can be used to surface decontaminate foods. This study investigated CP technology for the nonthermal inactivation of human norovirus surrogates, Tulane virus (TV) and murine norovirus (MNV), on the surface of blueberries. Blueberries (5 g) were weighed into sterile 4 oz. glass jars and inoculated with TV, 5 log PFU/g. Samples were treated with atmospheric CP for 0, 15, 30, 45, and 60 s at a working distance of 7.5 cm with 4 cubic feet/minute (cfm) of CP jet. Temperature readings were taken with an infrared camera prior to, and immediately following, CP treatments. In order to establish the impact of air flow during CP treatment (4 cfm), an additional 7 cfm jet of room temperature air was introduced from a separate nozzle. The experiment was repeated with 90 and 120 s as additional treatment time points. Viral titers were measured immediately after each treatment with a plaque assay using LLC-MK2 cells (TV) or RAW 264.7 cells (MNV). TV was significantly reduced 1.5 PFU/g compared to the control after treatment time of 45s, which was achieved regardless of temperature conditions. With the addition of 7 cfm of ambient air, the maximum log reduction for TV was 3.5 log PFU/g after 120s of treatment. MNV was significantly reduced by 0.5 log PFU/g compare to the control at 15s, and further treatment of MNV with ambient air brought the log reduction to greater than 5 log PFU/g at 90 s of treatment (Fig. 3). These results demonstrate that CP viral inactivation does not rely on thermal inactivation, and is therefore nonthermal in nature. With further optimization, CP may be used by food processors as a means of nonthermal inactivation of foodborne viruses. Published by Elsevier Ltd.

Differentiation of pancreatic ductal adenocarcinoma from chronic pancreatitis by PAM4 immunohistochemistry.

PubMed

Shi, Chanjuan; Merchant, Nipun; Newsome, Guy; Goldenberg, David M; Gold, David V

2014-02-01

PAM4 is a monoclonal antibody that shows high specificity for pancreatic ductal adenocarcinoma (PDAC) and its neoplastic precursor lesions. A PAM4-based serum immunoassay is able to detect 71% of early-stage patients and 91% with advanced disease. However, approximately 20% of patients diagnosed with chronic pancreatitis (CP) are also positive for circulating PAM4 antigen. The specificity of the PAM4 antibody is critical to the interpretation of the serum-based and immunohistochemical assays for detection of PDAC. To determine whether PAM4 can differentiate PDAC from nonneoplastic lesions of the pancreas. Tissue microarrays of PDAC (N = 43) and surgical specimens from CP (N = 32) and benign cystic lesions (N = 19) were evaluated for expression of the PAM4 biomarker, MUC1, MUC4, CEACAM5/6, and CA19-9. PAM4 and monoclonal antibodies (MAbs) to MUC1, MUC4, CEACAM5/6, and CA19-9 were each reactive with the majority of PDAC cases; however, PAM4 was the only monoclonal antibody not to react with adjacent, nonneoplastic parenchyma. Although PAM4 labeled 19% (6 of 32) of CP specimens, reactivity was restricted to pancreatic intraepithelial neoplasia associated with CP; inflamed tissues were negative in all cases. In contrast, MUC1, MUC4, CEACAM5/6, and CA19-9 were detected in 90%, 78%, 97%, and 100% of CP, respectively, with reactivity also present in nonneoplastic inflamed tissue. PAM4 was the only monoclonal antibody able to differentiate PDAC (and pancreatic intraepithelial neoplasia precursor lesions) from benign, nonneoplastic tissues of the pancreas. These results suggest the use of PAM4 for evaluation of tissue specimens, and support its role as an immunoassay for detection of PDAC.

Hemilability of the 1,2-Bis(dimethylphosphino)ethane (dmpe) Ligand in Cp*Mo(NO)(κ2-dmpe).

PubMed

Holmes, Aaron S; Patrick, Brian O; Levesque, Taleah M; Legzdins, Peter

2017-09-18

Reaction of Cp*Mo(NO)Cl 2 with 1 equiv of 1,2-bis(dimethylphosphino)ethane (dmpe) in THF at ambient temperature forms [Cp*Mo(NO)(Cl)(κ 2 -dmpe)]Cl (1), which is isolable as an analytically pure yellow powder in 65% yield. Further addition of 2 equiv of Cp 2 Co to 1 in CH 2 Cl 2 affords dark red Cp*Mo(NO)(κ 2 -dmpe) (2), which was isolated in 36% yield by recrystallization from Et 2 O at -30 °C. Reaction of a benzene solution of 2 with an equimolar amount of elemental sulfur results in the immediate production of dark blue (μ-S)[Cp*Mo(NO)(κ 1 -dmpeS)] 2 (3), which is a rare example of a bimetallic transition-metal complex bridged by only a single sulfur atom and involving Mo═S═Mo bonding. In contrast, reaction of 2 with an excess of sulfur in benzene results in the formation of Cp*Mo(NO)(η 2 -S 2 )(κ 1 -dmpeS) (4). Complex 4 can also be formed by the addition of elemental sulfur to 3, thereby indicating that 3 is a precursor to 4. Cp*Mo(NO)(κ 2 -dmpe) (2) also undergoes interesting transformations when treated with organic bromides. For instance, reaction of 2 with 5 equiv benzyl bromide in THF produces the bimetallic complex (μ-dmpe)[Cp*Mo(NO)Br 2 ] 2 (5) and bibenzyl after 4 d at 70 °C probably via radical intermediates. In contrast to its reaction with benzyl bromide, complex 2 forms [Mo(NO)Br 2 (κ 2 -dmpe)] 2 (6), olefin, alkane, and Cp*H when treated with 5 equiv of 1-bromopropane or 1-bromooctane in THF at 70 °C for 72 h. Interestingly, complex 2 does not display any reactivity with bromobenzene or 1-bromoadamantane even after being heated for several days at 70 °C. All new complexes were characterized by conventional spectroscopic and analytical methods, and the solid-state molecular structures of most of them were established by single-crystal X-ray crystallographic analyses.

LINE1 CpG-DNA Hypomethylation in Granulosa Cells and Blood Leukocytes Is Associated With PCOS and Related Traits.

PubMed

Sagvekar, Pooja; Mangoli, Vijay; Desai, Sadhana; Patil, Anushree; Mukherjee, Srabani

2017-04-01

Altered global DNA methylation is indicative of epigenomic instability concerning chronic diseases. Investigating its incidence and association with polycystic ovary syndrome (PCOS) is essential to understand the etiopathogenesis of this disorder. We assessed global DNA methylation differences in peripheral blood leukocytes (PBLs) and cumulus granulosa cells (CGCs) of controls and women with PCOS; and their association with PCOS and its traits. This study included a total of 102 controls and women with PCOS. Forty-one women undergoing controlled ovarian hyperstimulation (COH) and 61 women not undergoing COH were recruited from in vitro fertilization (IVF) and infertility clinics. DNA methylation was measured by ELISA for 5'-methyl-cytosine content and bisulfite sequencing of 5'-untranslated region (5'-UTR) of long interspersed nucleotide element-1 (LINE1/L1). Total 5'-methyl-cytosine and L1 methylation levels in PBLs and CGCs were similar between controls and women with PCOS. Methylation assessed at CpG sites of L1 5'-UTR revealed a single CpG-site (CpG-4) to be consistently hypomethylated in PBLs of both PCOS groups and CGCs of stimulated PCOS group. In unstimulated women, hypomethylation at CpG-4 was strongly associated with PCOS susceptibility, whereas in stimulated group it showed strong associations with PCOS and its hormonal traits. Furthermore, CGCs demonstrated consistent global and CpG-DNA hypomethylation relative to PBLs, irrespective of normal or disease states. Our study revealed strong association of single hypomethylated CpG-site with PCOS. Identification and characterization of more such methyl-CpG signatures in repetitive elements in larger study populations would provide valuable epigenetic insights into PCOS. Copyright © 2017 by the Endocrine Society

Strengthening Mechanisms in Nanostructured Al/SiCp Composite Manufactured by Accumulative Press Bonding

NASA Astrophysics Data System (ADS)

Amirkhanlou, Sajjad; Rahimian, Mehdi; Ketabchi, Mostafa; Parvin, Nader; Yaghinali, Parisa; Carreño, Fernando

2016-10-01

The strengthening mechanisms in nanostructured Al/SiCp composite deformed to high strain by a novel severe plastic deformation process, accumulative press bonding (APB), were investigated. The composite exhibited yield strength of 148 MPa which was 5 and 1.5 times higher than that of raw aluminum (29 MPa) and aluminum-APB (95 MPa) alloys, respectively. A remarkable increase was also observed in the ultimate tensile strength of Al/SiCp-APB composite, 222 MPa, which was 2.5 and 1.2 times greater than the obtained values for raw aluminum (88 MPa) and aluminum-APB (180 MPa) alloys, respectively. Analytical models well described the contribution of various strengthening mechanisms. The contributions of grain boundary, strain hardening, thermal mismatch, Orowan, elastic mismatch, and load-bearing strengthening mechanisms to the overall strength of the Al/SiCp microcomposite were 64.9, 49, 6.8, 2.4, 5.4, and 1.5 MPa, respectively. Whereas Orowan strengthening mechanism was considered as the most dominating strengthening mechanism in Al/SiCp nanocomposites, it was negligible for strengthening the microcomposite. Al/SiCp nanocomposite showed good agreement with quadratic summation model; however, experimental results exhibited good accordance with arithmetic and compounding summation models in the microcomposite. While average grain size of the composite reached 380 nm, it was less than 100 nm in the vicinity of SiC particles as a result of particle-stimulated nucleation mechanism.

Diphosphine- and CO-Induced Fragmentation of Chloride-bridged Dinuclear Complex and Cp*Ir(mu-Cl)(3)Re(CO)(3) and Attempted Synthesis of Cp*Ir(mu-Cl)(3)Mn(CO)(3): Spectroscopic Data and X-ray Diffraction Structures of the Pentamethylcyclopentadienyl Compounds [Cp*IrCl{(Z)-Ph2PCH = CHPPh2}][Cl]center dot 2CHCl(3) and Cp*Ir(CO)Cl-2

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hammons, Casey; Wang, Xiaoping; Nesterov, Vladimir

2010-01-01

The confacial bioctahedral compound Cp*Ir(mu-Cl)(3)Re(CO)(3) (1) undergoes rapid fragmentation in the presence of the unsaturated diphosphine ligand (Z)-Ph2PCH = CHPPh2 to give the mononuclear compounds [Cp*IrCl {(Z)-Ph2PCH = CHPPh2}][Cl] (2) and fac-ClRe(CO)(3)[(Z)-Ph2PCH = CHPPh2] (3). 2 has been characterized by H-1 and P-31 NMR spectroscopy and X-ray diffraction analysis. 2 center dot 2CHCl(3) crystallizes in the monoclinic space group C2/c, a = 35.023 (8) angstrom, b = 10.189 (2) angstrom, c = 24.003 (6) angstrom, b = 103.340 (3), V = 8,335 (3) angstrom 3, Z = 8, and d(calc) = 1.647 Mg/m(3); R = 0.0383, R-w = 0.1135 formore » 8,178 reflections with I> 2 sigma(I). The Ir(III) center in 2 exhibits a six-coordinate geometry and displays a chelating diphosphine group. Compound 1 reacts with added CO with fragmentation to yield the known compounds Cp*Ir(CO)Cl-2 (4) and ClRe(CO)(5) (5) in near quantitative yield by IR spectroscopy. Using the protocol established by our groups for the synthesis of 1, we have explored the reaction of [Cp*IrCl2](2) with ClMn(CO)(5) as a potential route to Cp*Ir(mu-Cl)(3)Mn(CO)(3); unfortunately, 4 was the only product isolated from this reaction. The solid-state structure of 4 was determined by X-ray diffraction analysis. 4 crystallizes in the triclinic space group P-1, a = 7.4059 (4) angstrom, b = 7.8940 (4) angstrom, c = 11.8488 (7) angstrom, alpha = 80.020 (1), beta = 79.758 (1), gamma = 68.631 (1), V = 630.34 (6) angstrom(3), Z = 2, and d(calc) = 2.246 Mg/m(3); R = 0.0126, R-w = 0.0329 for 2,754 reflections with I> 2 sigma(I). The expected three-legged piano-stool geometry in 4 has been crystallographically confirmed.« less

Physical properties of superbulky lanthanide metallocenes: synthesis and extraordinary luminescence of [Eu(II)(Cp(BIG))2] (Cp(BIG) = (4-nBu-C6H4)5-cyclopentadienyl).

PubMed

Harder, Sjoerd; Naglav, Dominik; Ruspic, Christian; Wickleder, Claudia; Adlung, Matthias; Hermes, Wilfried; Eul, Matthias; Pöttgen, Rainer; Rego, Daniel B; Poineau, Frederic; Czerwinski, Kenneth R; Herber, Rolfe H; Nowik, Israel

2013-09-09

The superbulky deca-aryleuropocene [Eu(Cp(BIG))2], Cp(BIG) = (4-nBu-C6H4)5-cyclopentadienyl, was prepared by reaction of [Eu(dmat)2(thf)2], DMAT = 2-Me2N-α-Me3Si-benzyl, with two equivalents of Cp(BIG)H. Recrystallizyation from cold hexane gave the product with a surprisingly bright and efficient orange emission (45% quantum yield). The crystal structure is isomorphic to those of [M(Cp(BIG))2] (M = Sm, Yb, Ca, Ba) and shows the typical distortions that arise from Cp(BIG)⋅⋅⋅Cp(BIG) attraction as well as excessively large displacement parameter for the heavy Eu atom (U(eq) = 0.075). In order to gain information on the true oxidation state of the central metal in superbulky metallocenes [M(Cp(BIG))2] (M = Sm, Eu, Yb), several physical analyses have been applied. Temperature-dependent magnetic susceptibility data of [Yb(Cp(BIG))2] show diamagnetism, indicating stable divalent ytterbium. Temperature-dependent (151)Eu Mössbauer effect spectroscopic examination of [Eu(Cp(BIG))2] was examined over the temperature range 93-215 K and the hyperfine and dynamical properties of the Eu(II) species are discussed in detail. The mean square amplitude of vibration of the Eu atom as a function of temperature was determined and compared to the value extracted from the single-crystal X-ray data at 203 K. The large difference in these two values was ascribed to the presence of static disorder and/or the presence of low-frequency torsional and librational modes in [Eu(Cp(BIG))2]. X-ray absorbance near edge spectroscopy (XANES) showed that all three [Ln(Cp(BIG))2] (Ln = Sm, Eu, Yb) compounds are divalent. The XANES white-line spectra are at 8.3, 7.3, and 7.8 eV, for Sm, Eu, and Yb, respectively, lower than the Ln2O3 standards. No XANES temperature dependence was found from room temperature to 100 K. XANES also showed that the [Ln(Cp(BIG))2] complexes had less trivalent impurity than a [EuI2(thf)x] standard. The complex [Eu(Cp(BIG))2] shows already at room temperature strong orange photoluminescence (quantum yield: 45 %): excitation at 412 nm (24,270 cm(-1)) gives a symmetrical single band in the emission spectrum at 606 nm (νmax =16495 cm(-1), FWHM: 2090 cm(-1), Stokes-shift: 2140 cm(-1)), which is assigned to a 4f(6)5d(1) → 4f(7) transition of Eu(II). These remarkable values compare well to those for Eu(II)-doped ionic host lattices and are likely caused by the rigidity of the [Eu(Cp(BIG))2] complex. Sharp emission signals, typical for Eu(III), are not visible. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effects of decreasing metabolizable protein and rumen-undegradable protein on milk production and composition and blood metabolites of Holstein dairy cows in early lactation.

PubMed

Bahrami-Yekdangi, H; Khorvash, M; Ghorbani, G R; Alikhani, M; Jahanian, R; Kamalian, E

2014-01-01

This study was conducted to evaluate the effects of decreasing dietary protein and rumen-undegradable protein (RUP) on production performance, nitrogen retention, and nutrient digestibility in high-producing Holstein cows in early lactation. Twelve multiparous Holstein lactating cows (2 lactations; 50 ± 7 d in milk; 47 kg/d of milk production) were used in a Latin square design with 4 treatments and 3 replicates (cows). Treatments 1 to 4 consisted of diets containing 18, 17.2, 16.4, and 15.6% crude protein (CP), respectively, with the 18% CP diet considered the control group. Rumen-degradable protein levels were constant across the treatments (approximately 10.9% on a dry matter basis), whereas RUP was gradually decreased. All diets were calculated to supply a postruminal Lys:Met ratio of about 3:1. Dietary CP had no significant effects on milk production or milk composition. In fact, 16.4% dietary CP compared with 18% dietary CP led to higher milk production; however, this effect was not significant. Feed intake was higher for 16.4% CP than for 18% CP (25.7 vs. 24.3 kg/d). Control cows had greater CP and RUP intakes, which resulted in higher concentrations of plasma urea nitrogen and milk urea nitrogen; cows receiving 16.4 and 15.6% CP, respectively, exhibited lower concentrations of milk urea nitrogen (15.2 and 15.1 vs. 17.3 mg/dL). The control diet had a significant effect on predicted urinary N. Higher CP digestibility was recorded for 18% CP compared with the other diets. Decreasing CP and RUP to 15.6 and 4.6% of dietary dry matter, respectively, had no negative effects on milk production or composition when the amounts of Lys and Met and the Lys:Met ratio were balanced. Furthermore, decreasing CP and RUP to 16.4 and 5.4%, respectively, increased dry matter intake. Copyright © 2014 American Dairy Science Association. Published by Elsevier Inc. All rights reserved.

Evaluation of an Automated Swallow-Detection Algorithm Using Visual Biofeedback in Healthy Adults and Head and Neck Cancer Survivors.

PubMed

Constantinescu, Gabriela; Kuffel, Kristina; Aalto, Daniel; Hodgetts, William; Rieger, Jana

2018-06-01

Mobile health (mHealth) technologies may offer an opportunity to address longstanding clinical challenges, such as access and adherence to swallowing therapy. Mobili-T ® is an mHealth device that uses surface electromyography (sEMG) to provide biofeedback on submental muscles activity during exercise. An automated swallow-detection algorithm was developed for Mobili-T ® . This study evaluated the performance of the swallow-detection algorithm. Ten healthy participants and 10 head and neck cancer (HNC) patients were fitted with the device. Signal was acquired during regular, effortful, and Mendelsohn maneuver saliva swallows, as well as lip presses, tongue, and head movements. Signals of interest were tagged during data acquisition and used to evaluate algorithm performance. Sensitivity and positive predictive values (PPV) were calculated for each participant. Saliva swallows were compared between HNC and controls in the four sEMG-based parameters used in the algorithm: duration, peak amplitude ratio, median frequency, and 15th percentile of the power spectrum density. In healthy participants, sensitivity and PPV were 92.3 and 83.9%, respectively. In HNC patients, sensitivity was 92.7% and PPV was 72.2%. In saliva swallows, HNC patients had longer event durations (U = 1925.5, p < 0.001), lower median frequency (U = 2674.0, p < 0.001), and lower 15th percentile of the power spectrum density [t(176.9) = 2.07, p < 0.001] than healthy participants. The automated swallow-detection algorithm performed well with healthy participants and retained a high sensitivity, but had lowered PPV with HNC patients. With respect to Mobili-T ® , the algorithm will next be evaluated using the mHealth system.

Characterization of active phosphorus surface sites at synthetic carbonate-free fluorapatite using single-pulse 1H, 31P, and 31P CP MAS NMR.

PubMed

Jarlbring, Mathias; Sandström, Dan E; Antzutkin, Oleg N; Forsling, Willis

2006-05-09

The chemically active phosphorus surface sites defined as PO(x), PO(x)H, and PO(x)H2, where x = 1, 2, or 3, and the bulk phosphorus groups of PO4(3-) at synthetic carbonate-free fluorapatite (Ca5(PO4)3F) have been studied by means of single-pulse 1H,31P, and 31P CP MAS NMR. The changes in composition and relative amounts of each surface species are evaluated as a function of pH. By combining spectra from single-pulse 1H and 31P MAS NMR and data from 31P CP MAS NMR experiments at varying contact times in the range 0.2-3.0 ms, it has been possible to distinguish between resonance lines in the NMR spectra originating from active surface sites and bulk phosphorus groups and also to assign the peaks in the NMR spectra to the specific phosphorus species. In the 31P CP MAS NMR experiments, the spinning frequency was set to 4.2 kHz; in the single-pulse 1H MAS NMR experiments, the spinning frequency was 10 kHz. The 31P CP MAS NMR spectrum of fluorapatite at pH 5.9 showed one dominating resonance line at 2.9 ppm assigned to originate from PO4(3-) groups and two weaker shoulder peaks at 5.4 and 0.8 ppm which were assigned to the unprotonated PO(x) (PO, PO2-, and PO3(2-)) and protonated PO(x)H (PO2H and PO3H-) surface sites. At pH 12.7, the intensity of the peak representing unprotonated PO(x) surface sites has increased 1.7% relative to the bulk peak, while the intensity of the peaks of the protonated species PO(x)H have decreased 1.4% relative to the bulk peak. At pH 3.5, a resonance peak at -4.5 ppm has appeared in the 31P CP MAS NMR spectrum assigned to the surface species PO(x)H2 (PO3H2). The results from the 1H MAS and 31P CP MAS NMR measurements indicated that H+, OH-, and physisorbed H2O at the surface were released during the drying process at 200 degrees C.

Antibodies to Staphylococcus aureus Serotype 8 Capsular Polysaccharide React with and Protect against Serotype 5 and 8 Isolates

PubMed Central

Park, Saeyoung; Gerber, Sabina

2014-01-01

Most Staphylococcus aureus isolates produce either a serotype 5 (CP5) or 8 (CP8) capsular polysaccharide, and the CP antigens are targets for vaccine development. Since CP5 and CP8 have similar trisaccharide repeating units, it is important to identify an epitope shared by both CP5 and CP8. To characterize cross-reactivity between CP5 and CP8, the immunogenicity of CP5 and CP8 conjugate vaccines in mice and rabbits was evaluated by serological assays. Immune sera were also tested for functional activity by in vitro opsonophagocytic-killing assays and a murine bacteremia model. Antibodies to the CP5-cross-reactive material 197 (CRM197) conjugate vaccine bound only to purified CP5. In contrast, antibodies to the CP8-CRM conjugate vaccine reacted with CP8 and (to a lesser extent) CP5. De-O-acetylation of CP5 increased its reactivity with CP8 antibodies. Moreover, CP8 antibodies bound to Pseudomonas aeruginosa O11 lipopolysaccharide, which has a trisaccharide repeating unit similar to that of the S. aureus CPs. CP8-CRM antibodies mediated in vitro opsonophagocytic killing of S. aureus expressing CP5 or CP8, whereas CP5-CRM antibodies were serotype specific. Passive immunization with antiserum to CP5-CRM or CP8-CRM protected mice against bacteremia induced by a serotype 5 S. aureus isolate, suggesting that CP8-CRM elicits antibodies cross-reactive to CP5. The identification of epitopes shared by CP5 and CP8 may inform the rational design of a vaccine to protect against infections caused by CP5- or CP8-producing strains of S. aureus. PMID:25245803

Mortality, cancer, and comorbidities associated with chronic pancreatitis: a Danish nationwide matched-cohort study.

PubMed

Bang, Ulrich Christian; Benfield, Thomas; Hyldstrup, Lars; Bendtsen, Flemming; Beck Jensen, Jens-Erik

2014-04-01

We aimed to assess the risk of death, cancer, and comorbidities among patients with alcoholic and nonalcoholic chronic pancreatitis (CP). We performed a nationwide retrospective cohort study, collecting data from Danish registries from 1995 through 2010. We evaluated the prevalences and incidences of death, cancers, and comorbidities among subjects with CP (cases) compared with age- and sex-matched individuals (controls). In total, 11,972 cases (71,814 person-years) and 119,720 controls (917,436 person-years) were included in the analysis. Hazard ratios (HR) were estimated by Cox proportional hazards regression. Forty-six percent of the cases died during the follow-up period, compared with 13.0% of controls (mean age, 63.7 vs 72.1 y; P < .0001), corresponding to a HR of 5.0 for CP (95% confidence interval [CI], 4.8-5.2). Cancer was a frequent cause of death among cases (10.2%) and controls (3.3%). Cancer (particularly pancreatic cancer) was a frequent cause of death among cases; the HR was 6.9 (95% CI, 7.5-11.8). Alcoholic CP did not produce a higher risk for cancer or death than nonalcoholic CP. Cerebrovascular disease (HR, 1.3; 95% CI, 1.2-1.4), chronic pulmonary disease (HR, 1.9; 95% CI, 1.8-2.1), ulcer disease (HR, 3.6; 95% CI, 3.3-3.9), diabetes (HR, 5.2; 95% CI, 5.0-5.6), and chronic renal disease (HR, 1.7; 95% CI, 1.5-1.9) occurred more frequently among patients with CP, but myocardial infarction did not (HR, 0.9; 95% CI, 0.8-1.0). Based on a Danish nationwide cohort study, individuals with CP are at higher risk for death from cancer (particularly pancreatic cancer) and have a higher incidence of comorbidities than people without CP. Copyright © 2014 AGA Institute. Published by Elsevier Inc. All rights reserved.

Preparation and reactivity of the heterobimetallic ReIr face-shared bioctahedral compounds Cp*Ir(mu-Cl)(3)Re(CO)(3) and Cp*Ir(mu-SC6H4Me-4)(3)Re(CO)(3): X-ray diffraction structures and redox behavior

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Xiaoping; Hammons, Casey; Richmond, Michael G.

2009-01-01

Thermolysis of the dinuclear compound [Cp*IrCl2](2) (1) with ClRe(CO)(5) (2) leads to the formation of the confacial bioctahedral compound Cp*Ir(mu-Cl)(3)Re(CO)(3) (3) in high yield. Whereas the substitution of the chloride ligands in 3 is observed on treatment with excess p-methylbenzenethiol to furnish the sulfido-bridged compound Cp*Ir(mu-SC6H4Me-4)(3)Re(CO)(3) (4), 3 undergoes fragmentation upon reaction with tertiary phosphines [PPh3 and P(OMe)(3)] to furnish the mononuclear compounds CP*IrCl2P and fac-ClRe-(CO3)P-2. Both 3 and 4 have been isolated and fully characterized in solution by IR and H-1 NMR spectroscopies, and their solid-state structures have been established by X-ray crystallography. The redox properties of 3 andmore » 4 have been explored by cyclic voltammetry, and the results are discussed relative to extended Huckel MO calculations.« less

Synthesis and structural characterization of PHP[(C(5)Me(4))(2)], a monodentate chiral phosphine derived from intramolecular C-C coupling of tetramethylcyclopentadienyl groups: an evaluation of steric and electronic properties.

PubMed

Shin, J H; Bridgewater, B M; Churchill, D G; Parkin, G

2001-10-22

The chiral monodentate phosphine PhP[(C(5)Me(4))(2)] is readily obtained by oxidation of the lithium complex Li(2)[PhP(C(5)Me(4))(2)] with I(2), which couples the two cyclopentadienyl groups to form a five-membered heterocyclic ring. The steric and electronic properties of PhP[(C(5)Me(4))(2)] have been evaluated by X-ray diffraction and IR spectroscopic studies on a variety of derivatives, including Ph[(C(5)Me(4))(2)]PE (E = S, Se), Cp*MCl(4)[P[(C(5)Me(4))(2)]Ph] (M = Mo, Ta), Ir[P[(C(5)Me(4))(2)]Ph](2)(CO)Cl, and CpFe(CO)[PhP[(C(5)Me(4))(2)

DNA methylation and transcription in a distal region upstream from the bovine AlphaS1 casein gene after once or twice daily milking.

PubMed

Nguyen, Minh; Boutinaud, Marion; Pétridou, Barbara; Gabory, Anne; Pannetier, Maëlle; Chat, Sophie; Bouet, Stephan; Jouneau, Luc; Jaffrezic, Florence; Laloë, Denis; Klopp, Christophe; Brun, Nicolas; Kress, Clémence; Jammes, Hélène; Charlier, Madia; Devinoy, Eve

2014-01-01

Once daily milking (ODM) induces a reduction in milk production when compared to twice daily milking (TDM). Unilateral ODM of one udder half and TDM of the other half, enables the study of underlying mechanisms independently of inter-individual variability (same genetic background) and of environmental factors. Our results show that in first-calf heifers three CpG, located 10 kb upstream from the CSN1S1 gene were methylated to 33, 34 and 28%, respectively, after TDM but these levels were higher after ODM, 38, 38 and 33%, respectively. These methylation levels were much lower than those observed in the mammary gland during pregnancy (57, 59 and 50%, respectively) or in the liver (74, 78 and 61%, respectively). The methylation level of a fourth CpG (CpG4), located close by (29% during TDM) was not altered after ODM. CpG4 methylation reached 39.7% and 59.5%, during pregnancy or in the liver, respectively. CpG4 is located within a weak STAT5 binding element, arranged in tandem with a second high affinity STAT5 element. STAT5 binding is only marginally modulated by CpG4 methylation, but it may be altered by the methylation levels of the three other CpG nearby. Our results therefore shed light on mechanisms that help to explain how milk production is almost, but not fully, restored when TDM is resumed (15.1 ± 0.2 kg/day instead of 16.2 ± 0.2 kg/day, p<0.01). The STAT5 elements are 100 bp away from a region transcribed in the antisense orientation, in the mammary gland during lactation, but not during pregnancy or in other reproductive organs (ovary or testes). We now need to clarify whether the transcription of this novel RNA is a consequence of STAT5 interacting with the CSN1S1 distal region, or whether it plays a role in the chromatin structure of this region.

Evidence against protective role of sex hormone estrogen in Cisplatin-induced nephrotoxicity in ovarectomized rat model.

PubMed

Pezeshki, Zahra; Nematbakhsh, Mehdi; Nasri, Hamid; Talebi, Ardeshir; Pilehvarian, Ali-Asghar; Safari, Tahereh; Eshraghi-Jazi, Fatemeh; Haghighi, Maryam; Ashrafi, Farzaneh

2013-01-01

Cisplatin (CP) is an effective drug in cancer therapy to treat the solid tumors, but it is accompanied with nephrotoxicity. The protective effect of estrogen in cardiovascular diseases is well-documented; but its nephron-protective effect against CP-induced nephrotoxicity is not completely understood. Thirty ovarectomized Wistar rats were divided in to five groups. Groups 1-3 received different doses of estradiol valerate (0.5, 2.5 and 10 mg/kg/week) in sesame oil for 4 weeks, and at the end of week 3, a single dose of CP (7 mg/kg, intraperitoneal [IP]) was administrated. Group 4 (positive control) received the same regimen as group 1-3 without estradiol without vehicle. The negative control group (Group 5) received sesame oil during the study. The animals were sacrificed 1 week after CP injection for histopathological studies. The serum level of blood urea nitrogen and creatinine, kidney tissue damage score (KTDS), kidney weight and percentage of body weight change in CP-treated groups significantly increased (P < 0.05), however, there were no significant differences detected between the estrogen-treated groups (Groups 1-3) and the positive control group (Group 4). Although, estradiol administration enhanced the serum level of nitrite, it was not affected by CP. Finally, significant correlation between KTDS and kidney weight was detected (r (2) = 0.63, P < 0.01). Estrogen is not nephron-protective against CP-induced nephrotoxicity. Moreover, it seems that the mechanism may be related to estrogen-induced oxidative stress in the kidney, which may promote the nephrotoxicity.

In silico cloning and characterization of the TGA (TGACG MOTIF-BINDING FACTOR) transcription factors subfamily in Carica papaya.

PubMed

Idrovo Espín, Fabio Marcelo; Peraza-Echeverria, Santy; Fuentes, Gabriela; Santamaría, Jorge M

2012-05-01

The TGA transcription factors belong to the subfamily of bZIP group D that play a major role in disease resistance and development. Most of the TGA identified in Arabidopsis interact with the master regulator of SAR, NPR1 that controls the expression of PR genes. As a first approach to determine the possible involvement of these transcription factors in papaya defense, we characterized Arabidopsis TGA orthologs from the genome of Carica papaya cv. SunUp. Six orthologs CpTGA1 to CpTGA6, were identified. The predicted CpTGA proteins were highly similar to AtTGA sequences and probably share the same DNA binding properties and transcriptional regulation features. The protein sequences alignment evidenced the presence of conserved domains, characteristic of this group of transcription factors. The phylogeny showed that CpTGA evolved into three different subclades associated with defense and floral development. This is the first report of basal expression patterns assessed by RT-PCR, from the whole subfamily of CpTGA members in different tissues from papaya cv. Maradol mature plants. Overall, CpTGA1, CpTGA3 CpTGA6 and CpTGA4 showed a basal expression in all tissues tested; CpTGA2 expressed strongly in all tissues except in petioles while CpTGA5 expressed only in petals and to a lower extent in petioles. Although more detailed studies in anthers and other floral structures are required, we suggest that CpTGA5 might be tissue-specific, and it might be involved in papaya floral development. On the other hand, we report here for the first time, the expression of the whole family of CpTGA in response to salicylic acid (SA). The expression of CpTGA3, CpTGA4 and CpTGA6 increased in response to SA, what would suggest its involvement in the SAR response in papaya. Copyright © 2012 Elsevier Masson SAS. All rights reserved.

Metal atom dynamics in superbulky metallocenes: a comparison of (Cp(BIG))2Sn and (Cp(BIG))2Eu.

PubMed

Harder, Sjoerd; Naglav, Dominik; Schwerdtfeger, Peter; Nowik, Israel; Herber, Rolfe H

2014-02-17

Cp(BIG)2Sn (Cp(BIG) = (4-n-Bu-C6H4)5cyclopentadienyl), prepared by reaction of 2 equiv of Cp(BIG)Na with SnCl2, crystallized isomorphous to other known metallocenes with this ligand (Ca, Sr, Ba, Sm, Eu, Yb). Similarly, it shows perfect linearity, C-H···C(π) bonding between the Cp(BIG) rings and out-of-plane bending of the aryl substituents toward the metal. Whereas all other Cp(BIG)2M complexes show large disorder in the metal position, the Sn atom in Cp(BIG)2Sn is perfectly ordered. In contrast, (119)Sn and (151)Eu Mößbauer investigations on the corresponding Cp(BIG)2M metallocenes show that Sn(II) is more dynamic and loosely bound than Eu(II). The large displacement factors in the group 2 and especially in the lanthanide(II) metallocenes Cp(BIG)2M can be explained by static metal disorder in a plane parallel to the Cp(BIG) rings. Despite parallel Cp(BIG) rings, these metallocenes have a nonlinear Cpcenter-M-Cpcenter geometry. This is explained by an ionic model in which metal atoms are polarized by the negatively charged Cp rings. The extent of nonlinearity is in line with trends found in M(2+) ion polarizabilities. The range of known calculated dipole polarizabilities at the Douglas-Kroll CCSD(T) level was extended with values (atomic units) for Sn(2+) 15.35, Sm(2+)(4f(6) (7)F) 9.82, Eu(2+)(4f(7) (8)S) 8.99, and Yb(2+)(4f(14) (1)S) 6.55. This polarizability model cannot be applied to predominantly covalently bound Cp(BIG)2Sn, which shows a perfectly ordered structure. The bent geometry of Cp*2Sn should therefore not be explained by metal polarizability but is due to van der Waals Cp*···Cp* attraction and (to some extent) to a small p-character component in the Sn lone pair.

Degradation of 4-chlorophenol and microbial diversity in soil inoculated with single Pseudomonas sp. CF600 and Stenotrophomonas maltophilia KB2.

PubMed

Nowak, Agnieszka; Mrozik, Agnieszka

2018-06-01

Soil contamination with chlorophenols is a serious problem all over the world due to their common use in different branches of industry and agriculture. The objective of this study was to determine whether bioaugmenting soil with single Pseudomonas sp. CF600 and Stenotrophomonas maltophilia KB2 and additional carbon sources such as phenol (P) and sodium benzoate (SB) could enhance the degradation of 4-chlorophenol (4-CP). During the degradation experiment, the number of bacteria as well as the structural and functional diversity of the soil microbial communities were determined. It was found that the most effective degradation of 4-CP in the soil was observed after it was inoculated with CF600 and the addition of SB. The biodegradation of five doses of 4-CP in this soil proceeded within 100 days. At the same time, the rate of the disappearance of 4-CP in the soil that had been bioaugmented with CF600 and contaminated with 4-CP and P was 5-6.5 times lower compared to its rate of disappearance in the soil that had been contaminated with 4-CP. The biodegradation of 4-CP in all of the treated and untreated soils was accompanied by a systematic decrease in the number of heterotrophic bacteria (THB) ranging between 13 and 40%. It was also proven that the tested aromatic compounds affected the soil microbial community structure through an increase in the marker fatty acids for Gram-negative bacteria (BG-) and fungi (F). The essential changes in the patterns of the fatty acid methyl esters (FAMEs) for the polluted soil included an increase in the fatty acid saturation and hydroxy fatty acid abundance. The obtained results also indicated that the introduction of CF600 into the soil contaminated with 4-CP and SB or P caused an increase in the functional diversity of the soil microorganisms. In contrast, in the soil that had been inoculated with KB2 and in the non-inoculated soil, the addition of 4-CP and P decreased the microbial activity. In conclusion, the inoculation of both strains into contaminated soil with aromatic compounds caused irreversible changes in the functional and structural diversity of the soil microbial communities. Copyright © 2018 Elsevier Ltd. All rights reserved.

Cerebral palsy after neonatal encephalopathy: do neonates with suspected asphyxia have worse outcomes?

PubMed

Garfinkle, Jarred; Wintermark, Pia; Shevell, Michael I; Oskoui, Maryam

2016-02-01

We sought to investigate how brain injury and severity, and neurological subtype of cerebral palsy (CP) differed in term-born children with CP after neonatal encephalopathy, between those with suspected birth asphyxia and those without. Using the Canadian CP Registry, which included 1001 children, those with CP born at ≥ 36 wks after moderate or severe neonatal encephalopathy, were dichotomized according to the presence or absence of suspected birth asphyxia. Gross Motor Function Classification System (GMFCS) scores, neurological subtypes, comorbidities, and magnetic resonance imaging findings were compared. Of the 147 term-born children with CP (82 males, 65 females; median age 37 months, interquartile range [IQR] 26-52.5) who after moderate or severe neonatal encephalopathy had the required outcome data, 61 (41%) met criteria for suspected birth asphyxia. They had a higher frequency of non-ambulatory GMFCS status (odds ratio [OR] 3.4, 95% confidence interval [CI] 1.72-6.8), spastic quadriplegia (OR 2.8, 95% CI 1.4-5.6), non-verbal communication skills impairment (OR 4.2, 95% CI 2.0-8.6), isolated deep grey matter injury (OR 4.1, 95% CI 1.8-9.5), a lower frequency of spastic hemiplegia (OR 0.17, 95% CI 0.07-0.42), focal injury (OR 0.20; 95% CI 0.04-0.93), and more comorbidities (p=0.017) than those who did not meet criteria. Term-born children who develop CP after neonatal encephalopathy with suspected birth asphyxia have a greater burden of disability than those without suspected birth asphyxia. © 2015 Mac Keith Press.

Effect of Pre-Oxidation Treatment of Nano-SiC Particulates on Microstructure and Mechanical Properties of SiC/Mg-8Al-1Sn Composites Fabricated by Powder Metallurgy Combined with Hot Extrusion

PubMed Central

Li, Chuan-Peng; Wang, Zhi-Guo; Zha, Min; Wang, Cheng; Yu, Hong-Chen; Wang, Hui-Yuan; Jiang, Qi-Chuan

2016-01-01

Nano-SiC particulates (n-SiCp) reinforced Mg-8Al-1Sn (AT81) composites with different pre-oxidation parameters were fabricated by powder metallurgy (P/M) process combined with hot extrusion. The effects of pre-oxidization treatment of n-SiCp on the microstructure and tensile properties of 0.5 vol % n-SiCp/AT81 composites were investigated accordingly. The distribution of n-SiCp with different pre-oxidation parameters was homogeneous in the composites. Moreover, it was found that a thin MgAl2O4 layer formed at the interface when the n-SiCp were pre-oxidized at 1073 K for 2 h, while the MgAl2O4 layer became much thicker with pre-oxidization temperature increasing to 1273 K for 2 h. After an appropriate pre-oxidization treatment of n-SiCp at 1073 K for 2 h, the as-extruded 0.5 vol % n-SiCp/AT81 composites exhibited an enhanced strength. It was found that the yield strength (YS) and ultimate tensile strength (UTS) increased from 168 MPa and 311 MPa to 255 MPa and 393 MPa compared with the as-extruded AT81 alloy, reflecting 51.8% and 26.4% increments, respectively. The improvement of mechanical properties should be mainly attributed to the grain refinement and homogeneous distribution of n-SiCp in the composites. Moreover, a well-bonded interface and the formation of an appropriate amount of interfacial product (MgAl2O4) benefited the material’s mechanical properties. PMID:28774083

Aqueous organometallic chemistry. 2. {sup 1}H NMR spectroscopic, synthetic, and structural study of the chemo- and diastereoselective reactions of [Cp{sup *}Rh(H{sub 2}O){sub 3}]{sup 2+} with nitrogen ligands as a function of pH

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ogo, Seiji; Chen, H.; Fish, R.H.

The reactions of a new Cp{sup *}Rh aqua synthon, [Cp{sup *}Rh(H{sub 2}O){sub 3}]{sup 2+} (1), at acidic pH values (2-6) with aniline (2), pyridine (3), and L-phenylalanine (4) have provided interesting chemo- and diastereoselectivities as studied by {sup 1}H NMR, FAB/MS, and single-crystal X-ray crystallography. The reaction of 2 and aqua complex 1, at pH values from 4 to 6, quantitatively provided [Cp{sup *}Rh({eta}{sup 6}-aniline)]{sup 2+} (5); the structure of 5 was unequivocally determined by a single-crystal X-ray analysis, which also showed an approximate 25% {eta}{sup 5} component. Compound 3 reacted with 1, at pH 2-6, to selectively provide [Cp{supmore » *}Rh({eta}{sup 1}-pyridine){sub n} (H{sub 2}O){sub 3-n}]{sup 2+} (n = 1-3) complexes 6a-c as a function of pH. Surprisingly, complex 1 reacted with 4, from pH 4 to 6, to provide only one diastereomer of the known cyclic trimer [(Cp{sup *}Rh)({mu}-{eta}{sup 1}-(OCO):{eta}{sup 2}-(N,OCO)-L-phe nylalanine)]{sub 3}{sup 3+} (7; S{sub C},S{sub C},S{sub C},S{sub Rh},S{sub Rh},S{sub Rh},) an example of a one-step, highly diastereoselective reaction in H{sub 2}O. 8 refs., 4 figs., 2 tabs.« less

Conserved Role of Intragenic DNA Methylation in Regulating Alternative Promoters

PubMed Central

Maunakea, Alika K.; Nagarajan, Raman P.; Bilenky, Mikhail; Ballinger, Tracy J.; D’Souza, Cletus; Fouse, Shaun D.; Johnson, Brett E.; Hong, Chibo; Nielsen, Cydney; Zhao, Yongjun; Turecki, Gustavo; Delaney, Allen; Varhol, Richard; Thiessen, Nina; Shchors, Ksenya; Heine, Vivi M.; Rowitch, David H.; Xing, Xiaoyun; Fiore, Chris; Schillebeeckx, Maximiliaan; Jones, Steven J.M.; Haussler, David; Marra, Marco A.; Hirst, Martin; Wang, Ting; Costello, Joseph F.

2014-01-01

While the methylation of DNA in 5′ promoters suppresses gene expression, the role of DNA methylation in gene bodies is unclear1–5. In mammals, tissue- and cell type-specific methylation is present in a small percentage of 5′ CpG island (CGI) promoters, while a far greater proportion occurs across gene bodies, coinciding with highly conserved sequences5–10. Tissue-specific intragenic methylation might reduce,3 or, paradoxically, enhance transcription elongation efficiency1,2,4,5. Capped analysis of gene expression (CAGE) experiments also indicate that transcription commonly initiates within and between genes11–15. To investigate the role of intragenic methylation, we generated a map of DNA methylation from human brain encompassing 24.7 million of the 28 million CpG sites. From the dense, high-resolution coverage of CpG islands, the majority of methylated CpG islands were revealed to be in intragenic and intergenic regions, while less than 3% of CpG islands in 5′ promoters were methylated. The CpG islands in all three locations overlapped with RNA markers of transcription initiation, and unmethylated CpG islands also overlapped significantly with trimethylation of H3K4, a histone modification enriched at promoters16. The general and CpG-island-specific patterns of methylation are conserved in mouse tissues. An in-depth investigation of the human SHANK3 locus17,18 and its mouse homologue demonstrated that this tissue-specific DNA methylation regulates intragenic promoter activity in vitro and in vivo. These methylation-regulated, alternative transcripts are expressed in a tissue and cell type-specific manner, and are expressed differentially within a single cell type from distinct brain regions. These results support a major role for intragenic methylation in regulating cell context-specific alternative promoters in gene bodies. PMID:20613842

Effects of concentrate crude protein content on nutrient digestibility, energy utilization, and methane emissions in lactating dairy cows fed fresh-cut perennial grass.

PubMed

Hynes, D N; Stergiadis, S; Gordon, A; Yan, T

2016-11-01

Although many studies have investigated mitigation strategies for methane (CH 4 ) output from dairy cows fed a wide variety of diets, research on the effects of concentrate crude protein (CP) content on CH 4 emissions from dairy cows offered fresh grass is limited. The present study was designed to evaluate the effects of cow genotype and concentrate CP level on nutrient digestibility, energy utilization, and CH 4 emissions in dairy cows offered fresh-grass diets. Twelve multiparous lactating dairy cows (6 Holstein and 6 Holstein × Swedish Red) were blocked into 3 groups for each breed and assigned to a low-, medium-, or high-CP concentrate diet [14.1, 16.1, and 18.1% CP on a dry matter (DM) basis, respectively], in a 3-period changeover study (25d per period). Total diets contained (DM basis) 32.8% concentrates and 67.2% perennial ryegrass, which was harvested daily. All measurements were undertaken during the final 6d of each period: digestibility measurements for 6d and calorimetric measurements in respiration chambers for 3d. Feed intake and milk production data were reported in a previous paper. We observed no significant interaction between concentrate CP level and cow genotype on any parameter. Concentrate CP level had no significant effect on any energy utilization parameter, except for urinary energy output, which was positively related to concentrate CP level. Similarly, concentrate CP content had no effect on CH 4 emission (g/d), CH 4 per kg feed intake, or nutrient digestibility. Cross breeding of Holstein cows significantly reduced gross energy, digestible energy, and metabolizable energy intake, heat production, and milk energy output. However, cow genotype had no significant effect on energy utilization efficiency or CH 4 parameters. Furthermore, the present study yielded a value for gross energy lost as CH 4 (5.6%) on fresh grass-based diets that was lower than the widely accepted value of 6.5%. The present findings indicate that reducing concentrate CP content from 18.1 to 14.1% may not be a successful way of alleviating CH 4 emissions from lactating dairy cows offered good-quality fresh grass, but grazing cows could be offered a low-CP concentrate without compromising energy utilization efficiency. Further research is needed to investigate whether larger differences in dietary CP content may yield positive results. Copyright © 2016 American Dairy Science Association. Published by Elsevier Inc. All rights reserved.

Quantitative analysis of the immunosuppressant CP-690,550 in whole blood by column-switching high-performance liquid chromatography and mass spectrometry detection.

PubMed

Paniagua, Ricardo; Campbell, Andrew; Changelian, Paul S; Reitz, Bruce A; Prakash, Chandra; Borie, Dominic C

2005-10-01

A fast and accurate method to quantify the new immunosuppressive JAK3 inhibitor CP-690,550 in whole blood using a dual-pump liquid chromatography-liquid chromatography-mass spectrometry (LC/LC-MS) system was developed and validated in nonhuman primate blood. Before injection, blood samples were prepared by precipitation with a reagent that included methanol and acetonitrile (30:70, vol/vol) along with the internal standard (CP-istd). Column-switching LC/LC-MS analysis used online extraction followed by separation on a C8 analytic column and MS detection of the [M + H] CP-690,550 (m/z = 313.1) and CP internal standard (m/z = 288.1). Linearity was always better than r = 0.99 (n = 7) for CP-690,550 (range 2.5-750 ng/mL), with a lower limit of quantification (LLOQ) of 2.5 ng/mL. The intrarun accuracy and precision ranged from 103.0% to 105.4% and 2.7% to 4.3%, respectively (n = 5), and the interday precision ranged from 8.7% to 11.1%, and the interday accuracy ranged from 98.1% to 103.8% of nominal values (n = 14). The injection repeatability for the method was 1.3% (n = 7). Except for the LLOQ, the intraday accuracy and precision in human blood were also within 15% (n = 5). The combination of simple sample preparation and short analytic run time of this sensitive procedure makes it effective for monitoring the concentration of CP-690,550 in whole blood in organ-transplant recipients.

Triple-decker sandwiches and related compounds of the first-row transition metals containing cyclopentadienyl and benzene rings.

PubMed

Liu, Haibo; Li, Qian-shu; Xie, Yaoming; King, R Bruce; Schaefer, Henry F

2010-08-12

The triple-decker sandwich compound trans-Cp(2)V(2)(eta(6):eta(6)-mu-C(6)H(6)) has been synthesized, as well as "slipped" sandwich compounds of the type trans-Cp(2)Co(2)(eta(4):eta(4)-mu-arene) and the cis-Cp(2)Fe(2)(eta(4):eta(4)-mu-C(6)R(6)) derivatives with an Fe-Fe bond (Cp = eta(5)-cyclopentadienyl). Theoretical studies show that the symmetrical triple-decker sandwich structures trans-Cp(2)M(2)(eta(6):eta(6)-mu-C(6)H(6)) are the global minima for M = Ti, V, and Mn but lie approximately 10 kcal/mol above the global minimum for M = Cr. The nonbonding M...M distances and spin states in these triple decker sandwich compounds can be related to the occupancies of the frontier bonding molecular orbitals. The global minimum for the chromium derivative is a singlet spin state cis-Cp(2)Cr(2)(eta(4):eta(4)-mu-C(6)H(6)) structure with a very short CrCr distance of 2.06 A, suggesting a formal quadruple bond. A triplet state cis-Cp(2)Cr(2)(eta(4):eta(4)-mu-C(6)H(6)) structure with a predicted Cr[triple bond]Cr distance of 2.26 A lies only approximately 3 kcal/mol above this global minimum. For the later transition metals the global minima are predicted to be cis-Cp(2)M(2)(eta(6):eta(6)-mu-C(6)H(6)) structures with a metal-metal bond, rather than triple decker sandwiches. These include singlet cis-Cp(2)Fe(2)(eta(4):eta(4)-mu-C(6)H(6)) with a predicted Fe=Fe double bond distance of 2.43 A, singlet cis-Cp(2)Co(2)(eta(3):eta(3)-mu-C(6)H(6)) with a predicted Co-Co single bond distance of 2.59 A, and triplet cis-Cp(2)Ni(2)(eta(3):eta(3)-mu-C(6)H(6)) with a predicted Ni-Ni distance of 2.71 A.

Geochemical particle fluxes in the Southern Indian Ocean seasonal ice zone: Prydz Bay region, East Antarctica

NASA Astrophysics Data System (ADS)

Pilskaln, C. H.; Manganini, S. J.; Trull, T. W.; Armand, L.; Howard, W.; Asper, V. L.; Massom, R.

2004-02-01

Time-series sediment traps were deployed between December 1998 and January 2000 and from March 2000 to February 2001 at two offshore Prydz Bay sites within the seasonal ice zone (SIZ) of the Southern Indian Ocean located between 62-63°S and 73-76°E to quantify seasonal biogeochemical particle fluxes. Samples were obtained from traps placed at 1400, 2400, and 3400 m during the first deployment year (PZB-1) and from 3300 m in the second deployment year (PZB-2). All geochemical export fluxes were highly seasonal with primary peaks occurring during the austral summer and relatively low fluxes prevailing through the winter months. Secondary flux peaks in mid-winter and in early spring were suggestive of small-scale, sea-ice break-up events and the spring retreat of seasonal ice, respectively. Biogenic silica represented over 70% (by weight) of the collected trap material and provided an annual opal export of 18 g m -2 to 1 km and 3-10 g m -2 to 3 km. POC fluxes supplied an annual export of approximately 1 g m -2, equal to the estimated ocean-wide average. Elevated particulate C org/C inorg and Si bio/C inorg molar ratios indicate a productive, diatom-dominated system, although consistently small fluxes of planktonic foraminifera and pteropod shells document a heterotrophic source of carbonate to deeper waters in the SIZ. The observation of high Si bio/C org ratios and the δ15N time-series data suggest enhanced rates of diatom-POC remineralization in the upper 1000 m relative to bioSiO 2. The occurrence in this region of a pronounced temperature minimum, associated with a strong pycnocline and subsurface particle maximum at 50-100 m, may represent a zone where sinking, diatom-rich particulates temporarily accumulate and POC is remineralized.

Mitomycin-C- or Cisplatin-Based Chemoradiotherapy for Anal Canal Carcinoma: Long-Term Results

DOE Office of Scientific and Technical Information (OSTI.GOV)

Olivatto, Luis O., E-mail: olivatto@inca.gov.b; Cabral, Vania; Rosa, Arthur

2011-02-01

Purpose: To evaluate the long-term efficacy of concurrent radiotherapy with mitomycin-C (MMC)-based or cisplatin (CP)-based combinations in a cohort of patients with locally advanced anal canal carcinoma. Methods and Materials: Between 1988 and 2000, 179 patients with locally advanced anal canal carcinoma were treated at the Instituto Nacional de Cancer with two cycles of chemotherapy during Weeks 1 and 5 of radiotherapy. 5-Fluorouracil (750 mg/m{sup 2} 120-hour infusion or 1,000 mg/m{sup 2} 96-hour infusion) plus CP (100 mg/m{sup 2}) on the first day of each cycle or MMC (10-15 mg/m{sup 2}) on the first day of Cycle 1 was administeredmore » concurrent with radiotherapy (total dose, 55-59.4 Gy). Of the 179 patients, 60% were included from a randomized trial initiated at the Instituto Nacional de Cancer in 1991 that compared concurrent chemoradiotherapy with MMC vs. CP. Results: The median follow-up for the whole chemoradiotherapy group was 83 months. The median patient age was 58 years, 57% had Stage T3-T4 tumors, and 35% had N-positive disease. The 5-year cumulative colostomy rate was not significantly different between the CP group (22%) and MMC group (29%; p = .28). The actuarial 10-year overall survival and disease-free survival rate for the CP group was 54% and 49% and for the MMC group was 52% and 53%, respectively (p = .32 and p = .92, respectively). On multivariate analysis, male gender (p = .042) and advanced Stage T3-T4 disease (p <.0001) were statistically significant for worse disease-free survival. Stage T3-T4 (p = .039) and N+ (p = .039) disease remained independently significant for overall survival. Conclusion: Long-term follow-up has confirmed the good results of chemoradiotherapy with CP plus 5-fluorouracil, which seem to provide results equivalent to those with MMC plus 5-fluorouracil.« less

Design and Development of a 5,000 Barrel Collapsible Fabric Petroleum Fuel Tank Assembly.

DTIC Science & Technology

1981-08-01

Compounds 4 Characteristics of Coated Fabric 24 5 Caracteristics of Bonded Fittings 26 6 Characteristics of Seams 27 v LIST OF APPENDICES PAGE APPENDIX "A...Foot Hose, 6 Feet CP24-0061 Elastofab Ground Cloth, Polyethlene CP92-0037 Read Plastics 1/2-Inch Rising Stem Gate Valve CP24-0018 Speakman 6-Inch...Distributing Company Easton Steel 83 North Main Street P. 0. Box 599 Yardley PA 19067 Easton MD 21601 SAS Gasket and Supply Co. Bronze & Plastic Specialties

Exploring the mechanism of action of the sperm-triggered calcium-wave pacemaker in ascidian zygotes.

PubMed

Carroll, Michael; Levasseur, Mark; Wood, Chris; Whitaker, Michael; Jones, Keith T; McDougall, Alex

2003-12-15

In ascidians, as in mammals, sperm trigger repetitive Ca2+-waves that originate from cortical pacemakers situated in the vegetal hemisphere of the zygotes. In ascidians, a vegetal protrusion termed the contraction pole (CP) acts as the Ca2+-wave pacemaker, but the mechanism that underlies the generation of a Ca2+-wave pacemaker is not known. Here, we tested four hypotheses to determine which factors at the CP are involved in setting the pace of the ascidian Ca2+-wave pacemaker: (1) localized Ca2+ influx; (2) accumulation of phosphatidylinositol (4,5)bisphosphate [PtdIns(4,5)P2]; (3) accumulation of cortical endoplasmic reticulum (cER); and (4) enrichment of the sperm activating factor. We developed a method of dynamically monitoring the location of the CP during fertilization using a plekstrin homology (PH) domain from phospholipase Cdelta1 coupled to green fluorescent protein (GFP) that binds PtdIns(4,5)P2. We found that eggs in Ca2+-free sea water displayed Ca2+ waves that originated from the CP, showing that enhanced CP Ca2+ influx does not determine the origin of the pacemaker. Also, disruption of the PH::GFP-labelled CP once it had formed did not dislodge the Ca2+-wave pacemaker from that site. Next, when we prevented the accumulation of cER at the CP, all of the Ca2+ waves came from the site of sperm-egg fusion and the frequency of Ca2+ oscillations was unaltered. These data show that local Ca2+ influx, the accumulation of PtdIns(4,5)P2 and cER at the CP are not required for Ca2+-wave pacemaker function and instead suggest that a factor associated with the sperm determines the site of the Ca2+-wave pacemaker. Finally, when we injected ascidian sperm extract into the centre of unfertilized ascidian eggs that had been treated with microfilament- and microtubule-disrupting drugs, all the Ca2+ waves still originated from near the plasma membrane, showing that the sperm factor does not require an intact cortex if it is enriched near the plasma membrane (PM). We suggest that the Ca2+-releasing sperm factor might be tethered near or on the PM and that following the cortical contraction, it is translocated to the vegetal CP, thus making that site act as a Ca2+-wave pacemaker.

Chloropicrin Emission Reduction by Soil Amendment with Biochar

PubMed Central

Wang, Qiuxia; Yan, Dongdong; Liu, Pengfei; Mao, Liangang; Wang, Dong; Fang, Wensheng; Li, Yuan; Ouyang, Canbin; Guo, Meixia; Cao, Aocheng

2015-01-01

Biochar has sorption capacity, and can be used to enhance the sequestration of volatile organic contaminants such as pesticides in soil. Chloropicrin (CP) is an important soil fumigant for the production of many fruit and vegetable crops, but its emissions must be minimized to reduce exposure risks and air pollution. The objective of this study was to determine the capacity of biochar to adsorb CP and the effect of biochar amendments to soil on CP emission, concentration in the soil gas phase, degradation in soil and CP bioactivity for controlling soil borne pests. CP emission and concentration in the soil air phase were measured from packed soil columns after fumigant injection at 20-cm depth and application of selected doses of biocharto the surface 5 cm soil. Laboratory incubation and fumigation experiments were conducted to determine the capacity of biochar to adsorb CP, the effects on CP degradation and, separately, CP’s bioactivity on soil borne pests in soil amended with biochar. Biochar amendment at 2% to 5% (w/w) greatly reduced total CP emission losses by 85.7% - 97.7% compared to fumigation without biochar. CP concentrations in the soil gas-phase, especially in the top 5 cm of soil, were reduced within 48 h following application. The half-life of CP decreased from 13.6 h to 6.4 h as the biochar rate increased from 0% to 5%. CP and its metabolite (dichloronitromethane) both degraded more rapidly in pure biochar than in soil. The biochar used in the present study had a maximum adsorption capacity for CP of less than 5 mg g-1. There were no negative effects on pathogen and nematode control when the biochar used in this study was less than 1% (on a weight basis) in soil. Biochar amendment to soil reduced the emissions of CP. CP concentrations in the top 5 cm of soil gas-phase were reduced. CP degradation was accelerated with the addition of biochar. The biochar used in the present study had a low adsorption capacity for CP. There were no negative effects on pathogen and nematode control when the biochar amendment rate was less than 1% (by weight). The findings would be useful for establishing guidelines for biochar use in soil fumigation. PMID:26075904

Observation of D^{0}→ρ^{0}γ and Search for CP Violation in Radiative Charm Decays.

PubMed

Nanut, T; Zupanc, A; Adachi, I; Aihara, H; Al Said, S; Asner, D M; Aulchenko, V; Aushev, T; Ayad, R; Babu, V; Badhrees, I; Bakich, A M; Bansal, V; Behera, P; Bhardwaj, V; Biswal, J; Bondar, A; Bozek, A; Bračko, M; Browder, T E; Červenkov, D; Chekelian, V; Chen, A; Cheon, B G; Chistov, R; Cho, K; Choi, S-K; Choi, Y; Cinabro, D; Dash, N; Di Carlo, S; Doležal, Z; Dutta, D; Eidelman, S; Farhat, H; Fast, J E; Ferber, T; Fulsom, B G; Gaur, V; Gabyshev, N; Garmash, A; Gillard, R; Goldenzweig, P; Golob, B; Hayasaka, K; Hayashii, H; Hou, W-S; Iijima, T; Inami, K; Inguglia, G; Ishikawa, A; Iwasaki, Y; Jacobs, W W; Jaegle, I; Joffe, D; Joo, K K; Julius, T; Kaliyar, A B; Kang, K H; Kawasaki, T; Kim, D Y; Kim, J B; Kim, K T; Kim, M J; Kim, S H; Kinoshita, K; Kodyš, P; Korpar, S; Krokovny, P; Kuhr, T; Kulasiri, R; Kuzmin, A; Kwon, Y-J; Lange, J S; Lee, I S; Li, C H; Li, L; Li, Y; Li Gioi, L; Libby, J; Liventsev, D; Lubej, M; Masuda, M; Matsuda, T; Matvienko, D; Miyabayashi, K; Miyata, H; Mizuk, R; Mohanty, G B; Moon, H K; Nakao, M; Nath, K J; Nayak, M; Nisar, N K; Nishida, S; Ogawa, S; Okuno, S; Pakhlov, P; Pakhlova, G; Pal, B; Park, C-S; Park, C W; Park, H; Paul, S; Pedlar, T K; Pesántez, L; Pestotnik, R; Petrič, M; Piilonen, L E; Prasanth, K; Pulvermacher, C; Rauch, J; Ritter, M; Rostomyan, A; Sakai, Y; Sandilya, S; Santelj, L; Sanuki, T; Sato, Y; Savinov, V; Schlüter, T; Schneider, O; Schnell, G; Schwanda, C; Schwartz, A J; Seino, Y; Senyo, K; Seon, O; Sevior, M E; Shebalin, V; Shen, C P; Shibata, T-A; Shiu, J-G; Shwartz, B; Solovieva, E; Stanič, S; Starič, M; Strube, J F; Stypula, J; Sumiyoshi, T; Takizawa, M; Tamponi, U; Tenchini, F; Trabelsi, K; Uchida, M; Uno, S; Ushiroda, Y; Varner, G; Vinokurova, A; Vorobyev, V; Vossen, A; Wang, C H; Wang, M-Z; Wang, P; Watanabe, Y; Widmann, E; Won, E; Yamaoka, J; Yamashita, Y; Yelton, J; Zhang, Z P; Zhilich, V; Zhukova, V; Zhulanov, V

2017-02-03

We report the first observation of the radiative charm decay D^{0}→ρ^{0}γ and the first search for CP violation in decays D^{0}→ρ^{0}γ, ϕγ, and K[over ¯]^{*0}(892)γ, using a data sample of 943  fb^{-1} collected with the Belle detector at the KEKB asymmetric-energy e^{+}e^{-} collider. The branching fraction is measured to be B(D^{0}→ρ^{0}γ)=(1.77±0.30±0.07)×10^{-5}, where the first uncertainty is statistical and the second is systematic. The obtained CP asymmetries A_{CP}(D^{0}→ρ^{0}γ)=+0.056±0.152±0.006, A_{CP}(D^{0}→ϕγ)=-0.094±0.066±0.001, and A_{CP}(D^{0}→K[over ¯]^{*0}γ)=-0.003±0.020±0.000 are consistent with no CP violation. We also present an improved measurement of the branching fractions B(D^{0}→ϕγ)=(2.76±0.19±0.10)×10^{-5} and B(D^{0}→K[over ¯]^{*0}γ)=(4.66±0.21±0.21)×10^{-4}.

Safety and Efficacy of Sorafenib in Patients with Hepatocellular Carcinoma (HCC) and Child-Pugh A versus B Cirrhosis

PubMed Central

Amadori, Dino; Santoro, Armando; Figer, Arie; De Greve, Jacques; Lathia, Chetan; Voliotis, Dimitris; Anderson, Sibyl; Moscovici, Marius; Ricci, Sergio

2011-01-01

ABSTRACT Background: We performed a retrospective analysis of data from a phase II study evaluating sorafenib in patients with advanced hepatocellular carcinoma (HCC) to assess differences in safety and efficacy based on Child-Pugh (CP) status (A/B). Methods: Patients received sorafenib 400 mg PO bid. We analyzed safety, pharmacokinetic (PK), and efficacy data in the two CP groups. Results: Ninety-eight patients were CP A; 38 were CP B, with a median duration of therapy of 4 and 1.8 months, respectively. Grade 3/4 adverse events in the CP A and B groups, respectively, included hyperbilirubinemia (14% and 53%), ascites (3% and 5%), and encephalopathy (3% and 13%). Median overall survival (OS) in the CP A group was 9.5 months, compared with 3.2 months in the CP B population. Responses were limited in both groups. AUC and Cmax values were comparable between the two groups. Conclusions: Due to the lack of randomization against placebo or no therapy in this study, it is unclear if the more frequent worsening of liver cirrhosis and outcome of CP B patients are drug related or due to disease progression, or both. As expected, outcome was poorer in patients with CP B than in those with CP A cirrhosis. The hyperbilirubinemia seen in both groups may be at least partly related to inhibition of UGT1A1 by sorafenib. PK profiles were similar in the two groups. More data are needed to confirm and more fully understand the safety and efficacy of sorafenib in patients with advanced HCC and CP B cirrhosis. PMID:21673874

Association between Promoter Methylation of Gene ERCC3 and Benzene Hematotoxicity.

PubMed

Zheng, Min; Lin, Feiliang; Hou, Fenxia; Li, Guilan; Zhu, Caiying; Xu, Peiyu; Xing, Caihong; Wang, Qianfei

2017-08-16

Benzene is a primary industrial chemical and a ubiquitous environmental pollutant. ERCC3 is a key player in nucleotide excision repair. Recent studies suggested that site-specific methylation is a possible mechanism of the transcriptional dysregulation by blocking transcription factors binding. We previously found that the average promoter methylation level of ERCC3 was increased in benzene-exposed workers. In order to test whether specific CpG sites of ERCC3 play an important role in benzene-induced epigenetic changes and whether the specific methylation patterns are associated with benzene hematotoxicity, we analyzed the promoter methylation levels of individual CpG sites, transcription factor binding motif and the correlation between aberrant CpG methylation and hematotoxicity in 76 benzene-exposed workers and 24 unexposed controls in China. Out of all the CpGs analyzed, two CpG units located 43 bp upstream and 99 bp downstream of the transcription start site of ERCC3 (CpG 2-4 and CpG 17-18, respectively), showed the most pronounced increase in methylation levels in benzene-exposed workers, compared with unexposed controls (Mean ± SD: 5.86 ± 2.77% vs. 4.92 ± 1.53%, p = 0.032; 8.45 ± 4.09% vs. 6.79 ± 2.50%, p = 0.024, respectively). Using the JASPAR CORE Database, we found that CpG 2-4 and CpG 17-18 were bound by three putative transcription factors (TFAP2A, E2F4 and MZF1). Furthermore, the methylation levels for CpG 2-4 were correlated negatively with the percentage of neutrophils ( β = -0.676, p = 0.005) in benzene-exposed workers. This study demonstrates that CpG-specific DNA methylation in the ERCC3 promoter region may be involved in benzene-induced epigenetic modification and it may contribute to benzene-induced hematotoxicity.

Association between Promoter Methylation of Gene ERCC3 and Benzene Hematotoxicity

PubMed Central

Lin, Feiliang; Hou, Fenxia; Li, Guilan; Zhu, Caiying; Xu, Peiyu; Xing, Caihong; Wang, Qianfei

2017-01-01

Benzene is a primary industrial chemical and a ubiquitous environmental pollutant. ERCC3 is a key player in nucleotide excision repair. Recent studies suggested that site-specific methylation is a possible mechanism of the transcriptional dysregulation by blocking transcription factors binding. We previously found that the average promoter methylation level of ERCC3 was increased in benzene-exposed workers. In order to test whether specific CpG sites of ERCC3 play an important role in benzene-induced epigenetic changes and whether the specific methylation patterns are associated with benzene hematotoxicity, we analyzed the promoter methylation levels of individual CpG sites, transcription factor binding motif and the correlation between aberrant CpG methylation and hematotoxicity in 76 benzene-exposed workers and 24 unexposed controls in China. Out of all the CpGs analyzed, two CpG units located 43 bp upstream and 99 bp downstream of the transcription start site of ERCC3 (CpG 2–4 and CpG 17–18, respectively), showed the most pronounced increase in methylation levels in benzene-exposed workers, compared with unexposed controls (Mean ± SD: 5.86 ± 2.77% vs. 4.92 ± 1.53%, p = 0.032; 8.45 ± 4.09% vs. 6.79 ± 2.50%, p = 0.024, respectively). Using the JASPAR CORE Database, we found that CpG 2–4 and CpG 17–18 were bound by three putative transcription factors (TFAP2A, E2F4 and MZF1). Furthermore, the methylation levels for CpG 2–4 were correlated negatively with the percentage of neutrophils (β = −0.676, p = 0.005) in benzene-exposed workers. This study demonstrates that CpG-specific DNA methylation in the ERCC3 promoter region may be involved in benzene-induced epigenetic modification and it may contribute to benzene-induced hematotoxicity. PMID:28813025

Study of CP asymmetry in B^{0}-B[over ¯]^{0} mixing with inclusive dilepton events.

PubMed

Lees, J P; Poireau, V; Tisserand, V; Grauges, E; Palano, A; Eigen, G; Stugu, B; Brown, D N; Kerth, L T; Kolomensky, Yu G; Lee, M J; Lynch, G; Koch, H; Schroeder, T; Hearty, C; Mattison, T S; McKenna, J A; So, R Y; Khan, A; Blinov, V E; Buzykaev, A R; Druzhinin, V P; Golubev, V B; Kravchenko, E A; Onuchin, A P; Serednyakov, S I; Skovpen, Yu I; Solodov, E P; Todyshev, K Yu; Lankford, A J; Mandelkern, M; Dey, B; Gary, J W; Long, O; Campagnari, C; Franco Sevilla, M; Hong, T M; Kovalskyi, D; Richman, J D; West, C A; Eisner, A M; Lockman, W S; Panduro Vazquez, W; Schumm, B A; Seiden, A; Chao, D S; Cheng, C H; Echenard, B; Flood, K T; Hitlin, D G; Miyashita, T S; Ongmongkolkul, P; Porter, F C; Röhrken, M; Andreassen, R; Huard, Z; Meadows, B T; Pushpawela, B G; Sokoloff, M D; Sun, L; Bloom, P C; Ford, W T; Gaz, A; Smith, J G; Wagner, S R; Ayad, R; Toki, W H; Spaan, B; Bernard, D; Verderi, M; Playfer, S; Bettoni, D; Bozzi, C; Calabrese, R; Cibinetto, G; Fioravanti, E; Garzia, I; Luppi, E; Piemontese, L; Santoro, V; Calcaterra, A; de Sangro, R; Finocchiaro, G; Martellotti, S; Patteri, P; Peruzzi, I M; Piccolo, M; Rama, M; Zallo, A; Contri, R; Lo Vetere, M; Monge, M R; Passaggio, S; Patrignani, C; Robutti, E; Bhuyan, B; Prasad, V; Adametz, A; Uwer, U; Lacker, H M; Dauncey, P D; Mallik, U; Chen, C; Cochran, J; Prell, S; Ahmed, H; Gritsan, A V; Arnaud, N; Davier, M; Derkach, D; Grosdidier, G; Le Diberder, F; Lutz, A M; Malaescu, B; Roudeau, P; Stocchi, A; Wormser, G; Lange, D J; Wright, D M; Coleman, J P; Fry, J R; Gabathuler, E; Hutchcroft, D E; Payne, D J; Touramanis, C; Bevan, A J; Di Lodovico, F; Sacco, R; Cowan, G; Bougher, J; Brown, D N; Davis, C L; Denig, A G; Fritsch, M; Gradl, W; Griessinger, K; Hafner, A; Schubert, K R; Barlow, R J; Lafferty, G D; Cenci, R; Hamilton, B; Jawahery, A; Roberts, D A; Cowan, R; Sciolla, G; Cheaib, R; Patel, P M; Robertson, S H; Neri, N; Palombo, F; Cremaldi, L; Godang, R; Sonnek, P; Summers, D J; Simard, M; Taras, P; De Nardo, G; Onorato, G; Sciacca, C; Martinelli, M; Raven, G; Jessop, C P; LoSecco, J M; Honscheid, K; Kass, R; Feltresi, E; Margoni, M; Morandin, M; Posocco, M; Rotondo, M; Simi, G; Simonetto, F; Stroili, R; Akar, S; Ben-Haim, E; Bomben, M; Bonneaud, G R; Briand, H; Calderini, G; Chauveau, J; Leruste, Ph; Marchiori, G; Ocariz, J; Biasini, M; Manoni, E; Pacetti, S; Rossi, A; Angelini, C; Batignani, G; Bettarini, S; Carpinelli, M; Casarosa, G; Cervelli, A; Chrzaszcz, M; Forti, F; Giorgi, M A; Lusiani, A; Oberhof, B; Paoloni, E; Perez, A; Rizzo, G; Walsh, J J; Lopes Pegna, D; Olsen, J; Smith, A J S; Faccini, R; Ferrarotto, F; Ferroni, F; Gaspero, M; Li Gioi, L; Pilloni, A; Piredda, G; Bünger, C; Dittrich, S; Grünberg, O; Hess, M; Leddig, T; Voß, C; Waldi, R; Adye, T; Olaiya, E O; Wilson, F F; Emery, S; Vasseur, G; Anulli, F; Aston, D; Bard, D J; Cartaro, C; Convery, M R; Dorfan, J; Dubois-Felsmann, G P; Dunwoodie, W; Ebert, M; Field, R C; Fulsom, B G; Graham, M T; Hast, C; Innes, W R; Kim, P; Leith, D W G S; Lewis, P; Lindemann, D; Luitz, S; Luth, V; Lynch, H L; MacFarlane, D B; Muller, D R; Neal, H; Perl, M; Pulliam, T; Ratcliff, B N; Roodman, A; Salnikov, A A; Schindler, R H; Snyder, A; Su, D; Sullivan, M K; Va'vra, J; Wisniewski, W J; Wulsin, H W; Purohit, M V; White, R M; Wilson, J R; Randle-Conde, A; Sekula, S J; Bellis, M; Burchat, P R; Puccio, E M T; Alam, M S; Ernst, J A; Gorodeisky, R; Guttman, N; Peimer, D R; Soffer, A; Spanier, S M; Ritchie, J L; Ruland, A M; Schwitters, R F; Wray, B C; Izen, J M; Lou, X C; Bianchi, F; De Mori, F; Filippi, A; Gamba, D; Lanceri, L; Vitale, L; Martinez-Vidal, F; Oyanguren, A; Villanueva-Perez, P; Albert, J; Banerjee, Sw; Beaulieu, A; Bernlochner, F U; Choi, H H F; King, G J; Kowalewski, R; Lewczuk, M J; Lueck, T; Nugent, I M; Roney, J M; Sobie, R J; Tasneem, N; Gershon, T J; Harrison, P F; Latham, T E; Band, H R; Dasu, S; Pan, Y; Prepost, R; Wu, S L

2015-02-27

We present a measurement of the asymmetry A_{CP} between same-sign inclusive dilepton samples ℓ^{+}ℓ^{+} and ℓ^{-}ℓ^{-} (ℓ=e, μ) from semileptonic B decays in ϒ(4S)→BB[over ¯] events, using the complete data set recorded by the BABAR experiment near the ϒ(4S) resonance, corresponding to 471×10^{6} BB[over ¯] pairs. The asymmetry A_{CP} allows comparison between the mixing probabilities P(B[over ¯]^{0}→B^{0}) and P(B^{0}→B[over ¯]^{0}), and therefore probes CP and T violation. The result, A_{CP}=[-3.9±3.5(stat)±1.9(syst)]×10^{-3}, is consistent with the standard model expectation.

Complexes of monocationic Group 13 elements with pentaphospha- and pentaarsaferrocene.

PubMed

Fleischmann, Martin; Welsch, Stefan; Krauss, Hannes; Schmidt, Monika; Bodensteiner, Michael; Peresypkina, Eugenia V; Sierka, Marek; Gröger, Christian; Scheer, Manfred

2014-03-24

Reactions of the sandwich complexes [Cp*Fe(η(5)-E5)] (Cp*=η(5)-C5Me5; E=P (1), As (2)) with the monovalent Group 13 metals Tl(+), In(+), and Ga(+) containing the weakly coordinating anion [TEF] ([TEF]=[Al{OC(CF3)3}4](-)) are described. Here, the one-dimensional coordination polymers [M(μ,η(5):η(1 -E5 FeCp*)3]n [TEF]n (E=P, M=Tl (3 a), In (3 b), Ga (3 c); E=As, M=Tl (4 a), In (4 b)) are obtained as sole products in good yields. All products were analyzed by single-crystal X-ray diffraction, revealing a similar assembly of the products with η(5)-bound E5 ligands and very weak σ-interactions between one P or As atom of the ring to the neighbored Group 13 metal cation. By exchanging the [TEF] anion of 4 a for the larger [FAl] anion ([FAl]=[FAl{OC6F10(C6F5)}3](-)), the coordination compound [Tl{(η(5)-As5)FeCp*}3][FAl] (5) without any σ-interactions of the As5-ring is obtained. All products are readily soluble in CH2 Cl2 and exhibit a dynamic coordination behavior in solution, which is supported by NMR spectroscopy and ESI-MS spectrometry as well as by osmometric molecular-weight determination. For a better understanding of the proceeding equilibrium DFT calculations of the cationic complexes were performed for the gas phase and in solution. Furthermore, the (31)P{(1)H} magic-angle spinning (MAS) NMR spectra of 3 a-c are presented and the first crystal structure of the starting material 2 was determined. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Insight into Oxide-Bridged Heterobimetallic Al/Zr Olefin Polymerization Catalysts.

PubMed

Boulho, Cédric; Zijlstra, Harmen S; Hofmann, Alexander; Budzelaar, Peter H M; Harder, Sjoerd

2016-11-21

Reaction of (TBBP)AlMe⋅THF with [Cp* 2 Zr(Me)OH] gave [(TBBP)Al(THF)-O-Zr(Me)Cp* 2 ] (TBBP=3,3',5,5'-tetra-tBu-2,2'-biphenolato). Reaction of [DIPPnacnacAl(Me)-O-Zr(Me)Cp 2 ] with [PhMe 2 NH] + [B(C 6 F 5 ) 4 ] - gave a cationic Al/Zr complex that could be structurally characterized as its THF adduct [(DIPPnacnac)Al(Me)-O-Zr(THF)Cp 2 ] + [B(C 6 F 5 ) 4 ] - (DIPPnacnac=HC[(Me)C=N(2,6-iPr 2 -C 6 H 3 )] 2 ). The first complex polymerizes ethene in the presence of an alkylaluminum scavenger but in the absence of methylalumoxane (MAO). The adduct cation is inactive under these conditions. Theoretical calculations show very high energy barriers (ΔG=40-47 kcal mol -1 ) for ethene insertion with a bridged AlOZr catalyst. This is due to an unfavorable six-membered-ring transition state, in which the methyl group bridges the metal and ethene with an obtuse metal-Me-C angle that prevents synchronized bond-breaking and making. A more-likely pathway is dissociation of the Al-O-Zr complex into an aluminate and the active polymerization catalyst [Cp* 2 ZrMe] + . © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hypermethylation of brain natriuretic peptide gene is associated with the risk of rheumatic heart disease

PubMed Central

Li, Ni; Zheng, Dawei; Sun, Lebo; Shi, Huoshun; Zhu, Xiuying; Xu, Guodong; Wang, Qinning; Zhu, Caimin

2016-01-01

To investigate the contribution of brain natriuretic peptide (BNP) promoter DNA methylation to the risk of rheumatic heart disease (RHD) and the influence of warfarin anticoagulant therapy on BNP methylation levels for RHD patients after surgery. BNP methylation levels were determined by bisulfite pyrosequencing from plasma samples of RHD patients compared with healthy controls. Several factors influencing the RHD patients were included like age, smoking and cholesterol levels. A fragment of five CG sites (CpG1–5) in the promoter region of BNP gene was measured. BNP gene hypermethylation was found in CpG4 and CpG5 in RHD patients compared with non-RHD controls. A significant difference was also observed between RHD patients with long-term administration of warfarin and RHD patients who had recently undergone an operation. Moreover, single CpG4 and CpG5 analysis revealed a significant increase in methylation levels in men. BNP gene body hypermethylation is associated with the risk of RHD, and also influenced by the warfarin anticoagulant therapy of RHD patients after surgery, which could represent novel and promising targets for therapeutic development. PMID:27920275

Comparison of the One-electron Oxidations of CO-Bridged vs Unbridged Bimetallic Complexes: Electron-transfer Chemistry of Os2Cp2(CO)4 and Os2Cp*2(μ-CO)2(CO)2 (Cp = η5-C5H5, Cp* = η5-C5Me5)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Laws, Derek R.; Bullock, R. Morris; Lee, Richmond

The one-electron oxidations of two dimers of half-sandwich osmium carbonyl complexes have been examined by electrochemistry, spectro-electrochemistry, and computational methods. The all-terminal carbonyl complex Os2Cp2(CO)4 (1, Cp = η5-C5H5) undergoes a reversible one-electron anodic reaction at E1/2 = 0.41 V vs ferrocene in CH2Cl2/0.05 M [NBu4][B(C6F5)4], giving a rare example of a metal-metal bonded radical cation unsupported by bridging ligands. The IR spectrum of 1+ is consistent with an approximately 1:1 mixture of anti and gauche structures for the 33 e- radical cation in which it has retained all-terminal bonding of the CO ligands. DFT calculations, including orbital-occupancy-perturbed Mayer bond-ordermore » analyses, show that the HOMOs of anti-1 and gauche-1 are metal-ligand delocalized. Removal of an electron from 1 has very little effect on the Os-Os bond order, accounting for the resistance of 1+ to heterolytic cleavage. The Os-Os bond distance is calculated to decrease by 0.10 Å and 0.06 Å as a consequence of one-electron oxidation of anti-1 and gauche-1, respectively. The CO-bridged complex Os2Cp*2(μ-CO)2(CO)2 (Cp* = η5-C5Me5), trans-2, undergoes a more facile oxidation, E1/2 = - 0.11 V, giving a persistent radical cation shown by solution IR analysis to preserve its bridged-carbonyl structure. However, ESR analysis of frozen solutions of 2+ is interpreted in terms of the presence of two isomers, most likely anti-2+ and trans-2+, at low temperature. Calculations show that the HOMO of trans-2 is highly delocalized over the metal-ligand framework, with the bridging carbonyls accounting for about half of the orbital makeup. The Os-Os bond order again changes very little with removal of an electron, and the Os-Os bond length actually undergoes minor shortening. Calculations suggest that the second isomer of 2+ has both the trans CO-bridged and the anti all-terminal CO structures. DRL and WEG acknowledge the support of the National Science Foundation under grant CHE-0808909. K-WH acknowledges financial support from KAUST. RMB thanks the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Biosciences and Geosciences for support. Pacific Northwest National Laboratory is a multiprogram national laboratory operated by Battelle for the U.S. Department of Energy. We thank Dr. S. I. Gorelsky for the discussion on the OOP analysis.« less

Zn0-CNTs-Fe3O4 catalytic in situ generation of H2O2 for heterogeneous Fenton degradation of 4-chlorophenol.

PubMed

Yang, Zhao; Gong, Xiao-Bo; Peng, Lin; Yang, Dan; Liu, Yong

2018-06-04

A novel Zn 0 -CNTs-Fe 3 O 4 composite was synthesized by the chemical co-precipitation combined with high sintering process at nitrogen atmosphere. The as-prepared composite was characterized by SEM, EDS, XRD, XPS, VSM and N 2 adsorption/desorption experiments. A novel heterogeneous Fenton-like system, composed of Zn 0 -CNTs-Fe 3 O 4 composite and dissolved oxygen (O 2 ) in solution, which can in situ generate H 2 O 2 and OH, was used for the degradation of 4-chlorophenol (4-CP). The influences of various operational parameters, including the initial pH, dosage of Zn 0 -CNTs-Fe 3 O 4 and initial concentration of 4-CP on the removal of 4-CP were investigated. The removal efficiencies of 4-CP and total organic carbon (TOC) were 99% and 57%, respectively, at the initial pH of 1.5, Zn 0 -CNTs-Fe 3 O 4 dosage of 2 g/L, 4-CP initial concentration of 50 mg/L and oxygen flow rate of 400 mL/min. Based on the results of the radical scavenger effect study, the hydroxyl radical was considered as the main reactive oxidants in Zn 0 -CNTs-Fe 3 O 4 /O 2 system and a possible degradation pathway of 4-CP was proposed. Copyright © 2018. Published by Elsevier Ltd.

Bioorganometallic chemistry. 5. Molecular recognition of aromatic amino acid guests by Cp{sup *} Rh-nucleobase/nucleoside/nucleotide cyclic trimer hosts in aqueous solution

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chen, H.; Maestre, M.F.; Fish, R.H.

We report what we believe is the first example of bioorganometallic hosts, 1-4, [Cp{sup *}Rh(9-methyladenine)]{sub 3}(OTf){sub 3} (1), [Cp{sup *}Rh(Me-5`-AMP)]{sub 3} (4), being able to recognize aromatic amino acid guests L-tryptophan (L-Trp) and L-phenylalanine (L-Phe) in aqueous media at pH 7. Results show that the molecular recognition of aromatic amino acids with bioorganometallic hosts 1-4 in aqueous solution, as studied by {sup 1}H NMR and NOE techniques, occurs predominately via a {pi}-{pi} interaction, and, in the case of L-Trp, additional electronic/hydrophobic interactions with hosts are possible. 7 refs., 1 fig., 1 tab.

Dispositions of enrofloxacin and its major metabolite ciprofloxacin in Thai swamp buffaloes

PubMed Central

RUENNARONG, Nitwarat; WONGPANIT, Kannika; SAKULTHAEW, Chainarong; GIORGI, Mario; KUMAGAI, Susumu; POAPOLATHEP, Amnart; POAPOLATHEP, Saranya

2015-01-01

Given the limited information available in this species, the aim of this study was to investigate the pharmacokinetic characteristics of enrofloxacin (ER) and its major metabolite ciprofloxacin (CP) in buffaloes, Bubalus bubalis. ER was administered intravenously (i.v.) or subcutaneously (s.c.) to buffaloes at doses of 5.0 and 7.5 mg/kg BW, and plasma, urine and fecal samples were collected until 48 hr post-administration. The concentrations of ER and CP in the plasma, urine and feces were analyzed using high-performance liquid chromatography equipped with a fluorescence detector. The plasma concentrations of ER and CP could be determined up to 24 hr and 32 hr after i.v. and s.c. administrations at doses of 5.0 and 7.5 mg/kg BW, respectively. CP concentrations were always lower than those of parental drug. The s.c. bioavailability of ER was 52.36 ± 4.24% and 72.12 ± 5.39% at doses of 5.0 and 7.5 mg/kg BW, respectively. Both ER and CP were detectable in urine and feces up to 24 hr. ER and CP were mainly excreted via the urine. Based on the pharmacokinetic data and PK-PD indices, s.c. administration of ER at doses of 5.0 and 7.5 mg/kg BW might be appropriate for the treatment of susceptible bacterial diseases in Thai swamp buffaloes. PMID:26596287

Photochemical insertion of alkynes into Cp sub 2 Fe sub 2 (CO) sub 2 (. mu. -CO) sub 2 : A mechanistic study by laser flash photolysis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bursten, B.E.; McKee, S.D.; Platz, M.S.

1989-04-26

Cp{sub 2}Fe{sub 2}(CO){sub 2}({mu}-CO){sub 2} (1: Cp = {eta}{sup 5}-C{sub 5}H{sub 5}) has a rich and diverse photochemistry, as evidenced by the plethora of synthetic and mechanistic studies of it in the literature. Early photochemical studies of 1 have demonstrated homolysis to the radical Cp(CO){sub 2}Fe{sup {sm bullet}} (2). Recent work on metal dimers indicates that a dinuclear species is formed concomitantly. Tyler, Schmidt, and Gray (TSG) first proposed that irradiation of 1 leads to the dinuclear species 3, which they suggested was the intermediate responsible for phosphine substitution. Research by other individuals has indicated that the substitutionally active speciesmore » is the CO-loss photoproduct CpFe({mu}-CO){sub 3}FeCp (4). The authors interest in the photochemistry of 1 stemmed from their theoretical studies on piano-stool dimers. One reaction of particular concern is the photochemical insertion of alkynes into 1 to yield dimetallacyclopentenone 5. On the basis of MO calculations, the authors proposed a possible LUMO-controlled mechanism for this reaction that involved alkyne addition to the TSG transition state 3, followed by CO loss. In this contribution, they report initial experimental studies which demonstrate that 4 is the photochemical intermediate responsible for this reaction. They consider this reaction to be a paradigm for photochemical substitution and insertion reaction in such systems.« less

Genome-Wide Associations between Genetic and Epigenetic Variation Influence mRNA Expression and Insulin Secretion in Human Pancreatic Islets

PubMed Central

Olsson, Anders H.; Volkov, Petr; Bacos, Karl; Dayeh, Tasnim; Hall, Elin; Nilsson, Emma A.; Ladenvall, Claes; Rönn, Tina; Ling, Charlotte

2014-01-01

Genetic and epigenetic mechanisms may interact and together affect biological processes and disease development. However, most previous studies have investigated genetic and epigenetic mechanisms independently, and studies examining their interactions throughout the human genome are lacking. To identify genetic loci that interact with the epigenome, we performed the first genome-wide DNA methylation quantitative trait locus (mQTL) analysis in human pancreatic islets. We related 574,553 single nucleotide polymorphisms (SNPs) with genome-wide DNA methylation data of 468,787 CpG sites targeting 99% of RefSeq genes in islets from 89 donors. We identified 67,438 SNP-CpG pairs in cis, corresponding to 36,783 SNPs (6.4% of tested SNPs) and 11,735 CpG sites (2.5% of tested CpGs), and 2,562 significant SNP-CpG pairs in trans, corresponding to 1,465 SNPs (0.3% of tested SNPs) and 383 CpG sites (0.08% of tested CpGs), showing significant associations after correction for multiple testing. These include reported diabetes loci, e.g. ADCY5, KCNJ11, HLA-DQA1, INS, PDX1 and GRB10. CpGs of significant cis-mQTLs were overrepresented in the gene body and outside of CpG islands. Follow-up analyses further identified mQTLs associated with gene expression and insulin secretion in human islets. Causal inference test (CIT) identified SNP-CpG pairs where DNA methylation in human islets is the potential mediator of the genetic association with gene expression or insulin secretion. Functional analyses further demonstrated that identified candidate genes (GPX7, GSTT1 and SNX19) directly affect key biological processes such as proliferation and apoptosis in pancreatic β-cells. Finally, we found direct correlations between DNA methylation of 22,773 (4.9%) CpGs with mRNA expression of 4,876 genes, where 90% of the correlations were negative when CpGs were located in the region surrounding transcription start site. Our study demonstrates for the first time how genome-wide genetic and epigenetic variation interacts to influence gene expression, islet function and potential diabetes risk in humans. PMID:25375650

Intramolecular and intermolecular N-H...C(5)H(5)(-) hydrogen bonding in magnesocene adducts of alkylamines. Implications for chemical vapor deposition using cyclopentadienyl source compounds.

PubMed

Xia, Aibing; Heeg, Mary Jane; Winter, Charles H

2002-09-25

Magnesocene adducts of alkylamines were prepared and characterized. Treatment of 3-amino-2,4-dimethylpentane, isopropylamine, tert-butylamine, benzylamine, or N-isopropylbenzylamine with magnesocene at ambient temperature in toluene afforded the amine adducts Cp2Mg(NH2CH(CH(CH3)2)2) (91%), Cp2Mg(NH2iPr) (80%), Cp2Mg(NH2tBu) (67%), Cp2Mg(NH2CH2Ph) (80%), and Cp2Mg(NH(CH(CH3)2)(CH2C6H5)) (91%). These adducts are stable at ambient temperature, and Cp2Mg(NH2CH(CH(CH3)2)2) can be sublimed at 60 degrees C/0.05 Torr without any evidence for reversion to magnesocene. The solid-state structure of Cp2Mg(NH2CH(CH(CH3)2)2) contains eta5- and eta2-cyclopentadienyl ligands, and the hydrogen atoms on the coordinated amine nitrogen atom participate in intramolecular and intermolecular hydrogen bonding to the eta2-cyclopentadienyl ligand. The observed hydrogen bonding is relevant to the path by which cyclopentadiene is eliminated from metal cyclopentadienyl CVD source compounds during film growth employing acidic element hydrides as co-reactants.

Regulation of the gut-specific carboxypeptidase: a study using the binary Gal4/UAS system in the mosquito Aedes aegypti

PubMed Central

Zhao, Bo; Kokoza, Vladimir A.; Saha, Tusar T.; Wang, Stephanie; Roy, Sourav; Raikhel, Alexander S.

2015-01-01

Pathogen transmission by mosquitoes is tightly linked to blood feeding which, in turn, is required for egg development. Studies of these processes would greatly benefit from genetic methods, such as the binary Gal4/UAS system. The latter has been well established for model organisms, but its availability is limited for mosquitoes. The objective of this study was to develop the blood-meal-activated, gut-specific Gal4/UAS system for the yellow-fever mosquito Aedes aegypti and utilize it to investigate the regulation of gut-specific gene expression. A 1.1-kb, 5' upstream region of the carboxypeptidase A (CP) gene was used to genetically engineer the CP-Gal4 driver mosquito line. The CP-Gal4 specifically activated the Enhanced Green Fluorescent Protein (EGFP) reporter only after blood feeding in the gut of the CP-Gal4>UAS-EGFP female Ae. aegypti. We used this system to study the regulation of CP gene expression. In vitro treatments with either amino acids (AAs) or insulin stimulated expression of the CP-Gal4>UAS-EGFP transgene; no effect was observed with 20-hydroxyecdysone (20E) treatments. The transgene activation by AAs and insulin was blocked by rapamycin, the inhibitor of the Target-of-Rapamycin kinase (TOR). RNA interference (RNAi) silence of the insulin receptor (IR) reduced the expression of the CP-Gal4>UAS-EGFP transgene. Thus, in vitro and in vivo experiments have revealed that insulin and TOR pathways control expression of the digestive enzyme CP. In contrast, 20E, the major regulator of post-blood-meal vitellogenic events in female mosquitoes, has no role in regulating the expression of this gene. This novel CP-Gal4/UAS system permits functional testing of midgut-specific genes that are involved in blood digestion and interaction with pathogens in Ae. aegypti mosquitoes. PMID:25152428

75 FR 57920 - Kerr-Philpott System

Federal Register 2010, 2011, 2012, 2013, 2014

2010-09-23

... schedules VA-1-B, VA-2-B, VA-3- B, VA-4-B, CP&L-1-B, CP&L-2-B, CP&L-3-B, CP&L-4-B, AP-1-B, AP-2-B, AP- 3-B..., CP&L-1-A, CP&L-2-A, CP&L-3-A, CP&L-4-A, AP-1-A, AP-2-A, AP-3-A, AP-4-A, NC-1-A, and Replacement-2... Schedules VA-1-A, VA-2-A, VA-3-A, VA-4-A, CP&L-1- A, CP&L-2-A, CP&L-3-A, CP&L-4-A, AP-1-A, AP-2-A, AP-3-A...

Reactivity of lanthanocene hydroxides toward ketene, isocyanate, lanthanocene alkyl, and triscyclopentadienyllanthanide complexes.

PubMed

Zhang, Chunmei; Liu, Ruiting; Zhang, Jie; Chen, Zhenxia; Zhou, Xigeng

2006-07-24

The reactivity of [Cp(2)Ln(mu-OH)(THF)]2 (Ln = Y (1), Er (2), Yb (3)) toward PhEtCCO, PhNCO, Cp3Ln, [Cp2Ln(mu-CH3)]2, and the LiCl adduct of Cp2Ln(n)Bu(THF)x was examined. In all cases, OH-centered reactivity is observed: complexes 1-3 react with PhEtCCO to form the O-H addition products [Cp2Ln(mu-eta1:eta2-O2CCHEtPh)]2 (Ln = Yb (5), Er (6), Y (7), respectively, for 1-3), whereas treatment of 1 with PhNCO affords the addition/CpH-elimination/rearrangement product [{Cp2Y(THF)}2(mu-eta2:eta2-O2CNPh)] (8), which contains an unusual PhNCO(2) dianionic ligand. Analogous compound [Cp2Ln(THF)]2(mu-eta2:eta2-O2CNPh) (Ln = Yb (9), Er (10)) and 8 can be obtained in a higher yield by treatment of [Cp2Ln(mu-OH)(THF)]2 with PhNCO followed by reaction with the corresponding Cp3Ln. However, attempts to prepare the corresponding heterobimetallic complex by reacting stoichiometric amounts of [Cp2Y(mu-OH)(THF)]2 with PhNCO followed by treating it with Cp3Yb are unsuccessful. Instead, only rearrangement products 8 and 9 are obtained. Furthermore, the reaction of 3 with [Cp2Yb(mu-CH3)]2 or Cp3Yb forms oxo-bridged compound [Cp2Yb(THF)]2(mu-O) (11), whereas the reaction of [Cp2ErCl]2 with Li(n)Bu followed by treatment with 2 affords unexpected mu-oxo lanthanocene cluster (Cp2Er)3(mu-OH)(mu3-O)(mu-Cl)Li(THF)4 (12). In contrast to 1 and 2, 3 shows a strong tendency to undergo the intermolecular elimination of CpH at room temperature, giving trinuclear species [Cp2Yb(mu-OH)]2[CpYb(THF)](mu3-O) (4). The single-crystal X-ray diffraction structures of 1, 2, and 4-12 are described. All the results offer an interesting contrast to transition- and main-metal hydroxide complexes.

Integrative Cardiac Health Project, Windber Research Institute

DTIC Science & Technology

2014-07-01

laparoscopically placed adjustable gastric banding (LAGB) baseline (5) and one year (5), control baseline (5) and one year (5). OD260/280 ratios...coverage and detection of 3-4 million CpG sites . All samples had a bisulfite conversion rate of >98.25%; number of CpG (methylated) sites per sample...methylation) and hyper-methylated (increasing methylation) sites in the three groups were identified. For LAGB patients, a heat map based on

Enhanced aerobic degradation of 4-chlorophenol with iron-nickel nanoparticles

NASA Astrophysics Data System (ADS)

Shen, Wenjuan; Mu, Yi; Wang, Bingning; Ai, Zhihui; Zhang, Lizhi

2017-01-01

In this study, we demonstrate that the bimetallic iron-nickel nanoparticles (nZVIN) possessed an enhanced performance in comparison with nanoscale zero-valent iron (nZVI) on aerobic degradation of 4-chlorophenol (4-CP). The 4-CP degradation rate constant in the aerobic nZVIN process (nZVIN/Air) was 5 times that in the classic nZVI counterpart system (nZVI/Air). Both reactive oxygen species measurement and inhibition experimental results suggested that hydroxyl radicals were the major active species contributed to aerobic 4-CP degradation with nZVI, on contrast, superoxide radicals predominated the 4-CP degradation in the nZVIN/Air process. High performance liquid chromatography and gas chromatography-mass spectrometer analysis indicated the intermediates of the nZVI/Air system were p-benzoquinone and hydroquinone, which were resulted from the bond cleavage between the chlorine and carbon atom in the benzene ring by hydroxyl radicals. However, the primary intermediates of 4-CP found in the nZVIN/Air system were phenol via the direct dechlorination by superoxide radicals, accompanying with the formation of chloride ions. On the base of experimental results, a superoxide radicals mediated enhancing mechanism was proposed for the aerobic degradation of 4-CP in the nZVIN/Air system. This study provides new insight into the role of bimetallic nickel on enhancing removal of organic pollutants with nZVI.

Influence of five home whitening gels and a remineralizing gel on the enamel and dentin ultrastructure and hardness.

PubMed

Pinheiro, Helena Burlamaqui; Cardoso, Paulo Eduardo Capel

2011-06-01

To investigate the influence of calcium phosphate enhanced home whitening agents on human enamel and dentin surface microhardness and ultramorphology. Five intact molars crowns were used for ultrastructural analysis and five for microhardness test. Each resulting coronal structure was cut in slices. After measuring baseline Knoop Hardness Number (KHN) of the enamel and dentin, the slices were divided into six experimental groups and one control (n= 5). G1= 15% carbamide peroxide (CP); G2= 16% CP; G3= Ca and PO4 (remineralizing agent); G4= 16% CP with Ca and PO4; G5= 7.5% hydrogen peroxide (HP) with Ca and PO4; G6=7.5% HP with Ca. After each daily session of treatment, specimens were stored in distilled water (37 degrees C) until the next session. Products were applied for 2 weeks, according to manufacturers' instructions. Additional KHN weredetermined. Conventional whitening agents (G1; G2) and the gel with Ca (G6), caused KHN decrease (P< 0.05).The remineralizing and whitening agents with Ca and PO4 (G3; G4; G5) did not change KHN. A change of morphology was observed on enamel and dentin surfaces in G1; G2; G5.

Enlisted MOS Suitable for the Physically Handicapped

DTIC Science & Technology

1958-12-01

highly motivated in a mobili- zation situation. The pr.mary reason for using this approach was the need for a standardized classification system which...the classification process. The solution was to consider all disabili- ties as "severe" and motivation to perform "good." Thus any individual disabled...MC+e0)H 4E-4)OOHe~~~ A A A P44 O0O)HCeHl H’d e (d *Hc.3d,4-4 HO) HQ .r4 to’- L 4 Xe 𔃺- H r4 Ps4 p) HO -i -i--I<-) rdr r d 90 P 4-- >< d0I - d a)0SoSS

The interaction of fentanyl on the Cp50 of propofol for loss of consciousness and skin incision.

PubMed

Smith, C; McEwan, A I; Jhaveri, R; Wilkinson, M; Goodman, D; Smith, L R; Canada, A T; Glass, P S

1994-10-01

We have previously demonstrated that the minimum alveolar concentration of isoflurane at 1 atm that is required to prevent movement in 50% of patients or animals exposed to a maximal noxious stimulus is markedly reduced by increasing fentanyl concentrations. Total intravenous anesthesia with propofol is increasing in popularity, yet the propofol concentrations required for total intravenous anesthesia or the interaction between propofol and fentanyl have not yet been defined. Propofol and fentanyl were administered via computer-assisted continuous infusion to provide pseudo-steady-state concentrations and allow equilibration between plasma-blood concentration and their biophase concentration. For the induction of anesthesia patients were randomly allocated to receive propofol only or propofol plus fentanyl 0.2, 0.8, 1.5, 3.0, and 4.5 ng/ml. In each group patients were randomized to target propofol concentrations of 1.5-10 micrograms/ml. At 7 and 10 min arterial blood samples were taken for subsequent measurement of propofol and fentanyl concentrations. At 10 min loss of consciousness was assessed by the patients' ability to respond to a simple verbal command. Thereafter a new target concentration of propofol was entered to ensure loss of consciousness, and succinylcholine was administered to facilitate tracheal intubation. Patients were rerandomized to a new target concentration of propofol (1-19 micrograms/ml) until skin incision. Before skin incision and 1 min after skin incision, arterial blood samples were again obtained for subsequent measurement of fentanyl and propofol concentrations. At skin incision and for 1 min the patient was observed for purposeful movement. Only samples in which the pre- and poststimulus drug concentrations were within 35% of each other were included. The propofol blood concentration at which 50% or 95% of patients did not respond to verbal command (Cp50s and Cp95s, respectively) and to skin incision (Cp50i and Cp95i, respectively), were calculated by logistic regression. There were 56 evaluable patients for calculating the propofol Cp50s and 53 patients for calculating the propofol Cp50i. For propofol alone the Cp50s was 3.3 micrograms/ml and the Cp95s 5.4 microgram/ml. Increasing fentanyl concentrations reduced the Cp50s (P = 0.03), and increasing age decreased the Cp50s (P = 0.04). For propofol alone the Cp50i was 15.2 (95% confidence interval 7.6-22.8) micrograms/ml and the Cp95i 27.4 micrograms/ml. Increasing fentanyl concentrations markedly reduced the Cp50i (P < 0.01), with a 50% reduction in Cp50i produced by 0.63 ng/ml fentanyl. The propofol Cp50i was decreased by 63% with 1 ng/ml fentanyl and 89% by 3 ng/ml fentanyl. At higher fentanyl concentrations the decrease in Cp50i was proportionally less, demonstrating a ceiling effect. We defined the propofol concentration required for loss of consciousness and showed that it is reduced by increasing fentanyl concentration and by increasing age. The propofol concentration (alone) adequate for skin incision is high but is markedly reduced by fentanyl. A ceiling effect in the Cp50i for propofol is seen with fentanyl concentrations greater than 3 ng/ml.

Nitrogen metabolism and route of excretion in beef feedlot cattle fed barley-based finishing diets varying in protein concentration and rumen degradability.

PubMed

Koenig, K M; Beauchemin, K A

2013-05-01

The objectives were to characterize the effects of supplemental CP concentration and ruminal degradability in barley-based finishing diets on microbial protein synthesis, ruminal fermentation and nutrient digestion, and route and chemical form of N excretion in beef cattle. Four Angus heifers (564 ± 18 kg BW) with ruminal and duodenal cannulas were used in an experiment designed as a 4 × 4 Latin square with four 28-d periods (9 d for diet adaptation and 19 d for measurements). The basal diet consisted of 9% barley silage and 91% barley-based concentrate (DM basis). Dietary treatments included the basal diet with no added protein (13% CP) or diets containing 14.5% CP by supplementation with urea (UREA), urea and canola meal (UREA+CM), or urea, corn gluten meal, and xylose-treated soybean meal (UREA+CGM+xSBM). Nutrient digestion was determined using Yb as a digesta flow marker and purine N as a microbial marker with the collection of ruminal, duodenal, and fecal samples over 5 d. The next week, total collections of feces and urine were performed for 5 d to quantify route and chemical form of N excretion. Feed offered was restricted (95% of ad libitum) and there was no effect of the dietary treatments on DMI (P = 0.55); therefore, N intake was less (P < 0.05) in heifers fed the 13% CP diets than the 14.5% CP diets. Supplemental RDP and RUP had no effect on ruminal NH3-N (P = 0.17), peptide N (P = 0.46), and VFA (P = 0.62) concentrations, flow of microbial (P = 0.69) and feed (P = 0.22) N, and ruminal and total tract nutrient digestibility (P ≥ 0.18). Nutrient digestion in the rumen and total tract averaged 75.4 ± 3.8% and 84.6 ± 0.9% for OM, 80.8 ± 3.6% and 95.8 ± 0.8% for starch, and 41.2 ± 7.9% and 60.4 ± 3.3% of intake for NDF, respectively. Daily output of N in feces (P = 0.91) and urine (P = 0.14) were not affected by the dietary treatments. Fecal N output averaged 19.9 ± 1.9% (P = 0.30) and urine N output averaged 44.1 ± 2.8% (P = 0.63) of N intake. Urea N output, however, was greater (P < 0.05) in heifers fed the 14.5% CP than the 13% CP diets and was the major form of N in urine (68.3% in heifers fed the 13% CP diet and 78.7 ± 2.9% in heifers fed the 14.5% CP diets; P < 0.10). Beef cattle fed barley-based finishing diets containing 13% CP do not require additional RDP or RUP to meet microbial or host N requirements. Barley-based finishing diets with no supplemental CP minimized urea N excretion and the potential loss of N from the system.

Measurement of the branching fractions and CP asymmetry of B--->D(0)((CP))K- decays with the BABAR detector.

PubMed

Aubert, B; Barate, R; Boutigny, D; Gaillard, J-M; Hicheur, A; Karyotakis, Y; Lees, J P; Robbe, P; Tisserand, V; Zghiche, A; Palano, A; Pompili, A; Chen, J C; Qi, N D; Rong, G; Wang, P; Zhu, Y S; Eigen, G; Ofte, I; Stugu, B; Abrams, G S; Borgland, A W; Breon, A B; Brown, D N; Button-Shafer, J; Cahn, R N; Charles, E; Day, C T; Gill, M S; Gritsan, A V; Groysman, Y; Jacobsen, R G; Kadel, R W; Kadyk, J; Kerth, L T; Kolomensky, Yu G; Kukartsev, G; LeClerc, C; Levi, M E; Lynch, G; Mir, L M; Oddone, P J; Orimoto, T J; Pripstein, M; Roe, N A; Romosan, A; Ronan, M T; Shelkov, V G; Telnov, A V; Wenzel, W A; Ford, K; Harrison, T J; Hawkes, C M; Knowles, D J; Morgan, S E; Penny, R C; Watson, A T; Watson, N K; Goetzen, K; Koch, H; Lewandowski, B; Pelizaeus, M; Peters, K; Schmuecker, H; Steinke, M; Boyd, J T; Chevalier, N; Cottingham, W N; Kelly, M P; Latham, T E; Mackay, C; Wilson, F F; Abe, K; Cuhadar-Donszelmann, T; Hearty, C; Mattison, T S; McKenna, J A; Thiessen, D; Kyberd, P; McKemey, A K; Teodorescu, L; Blinov, V E; Bukin, A D; Golubev, V B; Ivanchenko, V N; Kravchenko, E A; Onuchin, A P; Serednyakov, S I; Skovpen, Yu I; Solodov, E P; Yushkov, A N; Best, D; Bruinsma, M; Chao, M; Eschrich, I; Kirkby, D; Lankford, A J; Mandelkern, M; Mommsen, R K; Roethel, W; Stoker, D P; Buchanan, C; Hartfiel, B L; Gary, J W; Shen, B C; Wang, K; Del Re, D; Hadavand, H K; Hill, E J; MacFarlane, D B; Paar, H P; Rahatlou, Sh; Sharma, V; Berryhill, J W; Campagnari, C; Dahmes, B; Kuznetsova, N; Levy, S L; Long, O; Lu, A; Mazur, M A; Richman, J D; Verkerke, W; Beck, T W; Beringer, J; Eisner, A M; Heusch, C A; Lockman, W S; Schalk, T; Schmitz, R E; Schumm, B A; Seiden, A; Turri, M; Walkowiak, W; Williams, D C; Wilson, M G; Albert, J; Chen, E; Dubois-Felsmann, G P; Dvoretskii, A; Hitlin, D G; Narsky, I; Piatenko, T; Porter, F C; Ryd, A; Samuel, A; Yang, S; Jayatilleke, S; Mancinelli, G; Meadows, B T; Sokoloff, M D; Abe, T; Blanc, F; Bloom, P; Chen, S; Clark, P J; Ford, W T; Nauenberg, U; Olivas, A; Rankin, P; Roy, J; Smith, J G; Van Hoek, W C; Zhang, L; Harton, J L; Hu, T; Soffer, A; Toki, W H; Wilson, R J; Zhang, J; Aleksan, R; Emery, S; Gaidot, A; Ganzhur, S F; Giraud, P-F; Hamel De Monchenault, G; Kozanecki, W; Langer, M; Legendre, M; London, G W; Mayer, B; Schott, G; Vasseur, G; Yeche, Ch; Zito, M; Altenburg, D; Brandt, T; Brose, J; Colberg, T; Dickopp, M; Hauke, A; Lacker, H M; Maly, E; Müller-Pfefferkorn, R; Nogowski, R; Otto, S; Schubert, J; Schubert, K R; Schwierz, R; Spaan, B; Bernard, D; Bonneaud, G R; Brochard, F; Cohen-Tanugi, J; Grenier, P; Thiebaux, Ch; Vasileiadis, G; Verderi, M; Khan, A; Lavin, D; Muheim, F; Playfer, S; Swain, J E; Andreotti, M; Azzolini, V; Bettoni, D; Bozzi, C; Calabrese, R; Cibinetto, G; Luppi, E; Negrini, M; Piemontese, L; Sarti, A; Treadwell, E; Anulli, F; Baldini-Ferroli, R; Calcaterra, A; De Sangro, R; Falciai, D; Finocchiaro, G; Patteri, P; Peruzzi, I M; Piccolo, M; Zallo, A; Buzzo, A; Capra, R; Contri, R; Crosetti, G; Lo Vetere, M; Macri, M; Monge, M R; Passaggio, S; Patrignani, C; Robutti, E; Santroni, A; Tosi, S; Bailey, S; Morii, M; Won, E; Dubitzky, R S; Langenegger, U; Bhimji, W; Bowerman, D A; Dauncey, P D; Egede, U; Gaillard, J R; Morton, G W; Nash, J A; Sanders, P; Taylor, G P; Grenier, G J; Lee, S-J; Mallik, U; Cochran, J; Crawley, H B; Lamsa, J; Meyer, W T; Prell, S; Rosenberg, E I; Yi, J; Biasini, M; Pioppi, M; Davier, M; Grosdidier, G; Höcker, A; Laplace, S; Le Diberder, F; Lepeltier, V; Lutz, A M; Petersen, T C; Plaszczynski, S; Schune, M H; Tantot, L; Wormser, G; Brigljević, V; Cheng, C H; Lange, D J; Wright, D M; Bevan, A J; Fry, J R; Gabathuler, E; Gamet, R; Kay, M; Payne, D J; Sloane, R J; Touramanis, C; Back, J J; Cormack, C M; Harrison, P F; Shorthouse, H W; Vidal, P B; Brown, C L; Cowan, G; Flack, R L; Flaecher, H U; George, S; Green, M G; Kurup, A; Marker, C E; McMahon, T R; Ricciardi, S; Salvatore, F; Vaitsas, G; Winter, M A; Brown, D; Davis, C L; Allison, J; Barlow, N R; Barlow, R J; Hart, P A; Hodgkinson, M C; Jackson, F; Lafferty, G D; Lyon, A J; Weatherall, J H; Williams, J C; Farbin, A; Jawahery, A; Kovalskyi, D; Lae, C K; Lillard, V; Roberts, D A; Blaylock, G; Dallapiccola, C; Flood, K T; Hertzbach, S S; Kofler, R; Koptchev, V B; Moore, T B; Saremi, S; Staengle, H; Willocq, S; Cowan, R; Sciolla, G; Taylor, F; Yamamoto, R K; Mangeol, D J J; Patel, P M; Robertson, S H; Lazzaro, A; Palombo, F; Bauer, J M; Cremaldi, L; Eschenburg, V; Godang, R; Kroeger, R; Reidy, J; Sanders, D A; Summers, D J; Zhao, H W; Brunet, S; Cote-Ahern, D; Taras, P; Nicholson, H; Raven, G; Wilden, L; Cartaro, C; Cavallo, N; De Nardo, G; Fabozzi, F; Gatto, C; Lista, L; Paolucci, P; Piccolo, D; Sciacca, C; Jessop, C P; LoSecco, J M; Gabriel, T A; Brau, B; Gan, K K; Honscheid, K; Hufnagel, D; Kagan, H; Kass, R; Pulliam, T; Wong, Q K; Brau, J; Frey, R; Potter, C T; Sinev, N B; Strom, D; Torrence, E; Colecchia, F; Dorigo, A; Galeazzi, F; Margoni, M; Morandin, M; Posocco, M; Rotondo, M; Simonetto, F; Stroili, R; Tiozzo, G; Voci, C; Benayoun, M; Briand, H; Chauveau, J; David, P; De la Vaissière, Ch; Del Buono, L; Hamon, O; John, M J J; Leruste, Ph; Ocariz, J; Pivk, M; Roos, L; Stark, J; T'Jampens, S; Therin, G; Manfredi, P F; Re, V; Behera, P K; Gladney, L; Guo, Q H; Panetta, J; Angelini, C; Batignani, G; Bettarini, S; Bondioli, M; Bucci, F; Calderini, G; Carpinelli, M; Del Gamba, V; Forti, F; Giorgi, M A; Lusiani, A; Marchiori, G; Martinez-Vidal, F; Morganti, M; Neri, N; Paoloni, E; Rama, M; Rizzo, G; Sandrelli, F; Walsh, J; Haire, M; Judd, D; Paick, K; Wagoner, D E; Cavoto, G; Danielson, N; Elmer, P; Lu, C; Miftakov, V; Olsen, J; Smith, A J S; Tanaka, H A; Bellini, F; Faccini, R; Ferrarotto, F; Ferroni, F; Gaspero, M; Mazzoni, M A; Morganti, S; Pierini, M; Piredda, G; Safai Tehrani, F; Voena, C; Christ, S; Wagner, G; Waldi, R; Adye, T; De Groot, N; Franek, B; Geddes, N I; Gopal, G P; Olaiya, E O; Xella, S M; Purohit, M V; Weidemann, A W; Yumiceva, F X; Aston, D; Bartoldus, R; Berger, N; Boyarski, A M; Buchmueller, O L; Convery, M R; Coupal, D P; Dong, D; Dorfan, J; Dujmic, D; Dunwoodie, W; Field, R C; Glanzman, T; Gowdy, S J; Grauges-Pous, E; Hadig, T; Halyo, V; Hryn'ova, T; Innes, W R; Kelsey, M H; Kim, P; Kocian, M L; Leith, D W G S; Libby, J; Luitz, S; Luth, V; Lynch, H L; Marsiske, H; Messner, R; Muller, D R; O'Grady, C P; Ozcan, V E; Perazzo, A; Perl, M; Petrak, S; Ratcliff, B N; Roodman, A; Salnikov, A A; Schindler, R H; Schwiening, J; Simi, G; Snyder, A; Soha, A; Stelzer, J; Su, D; Sullivan, M K; Va'vra, J; Wagner, S R; Weaver, M; Weinstein, A J R; Wisniewski, W J; Wright, D H; Young, C C; Burchat, P R; Edwards, A J; Meyer, T I; Petersen, B A; Roat, C; Ahmed, M; Ahmed, S; Alam, M S; Ernst, J A; Saeed, M A; Saleem, M; Wappler, F R; Bugg, W; Krishnamurthy, M; Spanier, S M; Eckmann, R; Kim, H; Ritchie, J L; Schwitters, R F; Izen, J M; Kitayama, I; Lou, X C; Ye, S; Bianchi, F; Bona, M; Gallo, F; Gamba, D; Borean, C; Bosisio, L; Della Ricca, G; Dittongo, S; Grancagnolo, S; Lanceri, L; Poropat, P; Vitale, L; Vuagnin, G; Panvini, R S; Banerjee, Sw; Brown, C M; Fortin, D; Jackson, P D; Kowalewski, R; Roney, J M; Band, H R; Dasu, S; Datta, M; Eichenbaum, A M; Johnson, J R; Kutter, P E; Li, H; Liu, R; Di Lodovico, F; Mihalyi, A; Mohapatra, A K; Pan, Y; Prepost, R; Sekula, S J; von Wimmersperg-Toeller, J H; Wu, J; Wu, S L; Yu, Z; Neal, H

2004-05-21

We present a study of B--->D(0)(CP)K- decays, where D(0)(CP) is reconstructed in CP-even channels, based on a sample of 88.8 x 10(6) Upsilon(4S)-->BB decays collected with the BABAR detector at the PEP-II e(+)e(-) storage ring. We measure the ratio of Cabibbo-suppressed to Cabibbo-favored branching fractions B(B--->D(0)(CP)K-)/B(B--->D(0)(CP)pi(-))=[8.8+/-1.6(stat)+/-0.5(syst)]x10(-2) and the CP asymmetry A(CP)=0.07+/-0.17(stat)+/-0.06(syst). We also measure B(B--->D0K-)/B(B--->D0pi(-))=[8.31+/-0.35(stat)+/-0.20(syst)]x10(-2) using a sample of 61.0 x 10(6) BB pairs.

Infrared matrix-isolation and theoretical studies of the reactions of ferrocene with ozone.

PubMed

Kugel, Roger W; Pinelo, Laura F; Ault, Bruce S

2015-03-19

The reactions between ferrocene (Cp2Fe) (2a) and ozone (O3) were studied using low-temperature matrix-isolation techniques coupled with theoretical density functional theory (DFT) calculations. Co-deposition of Ar/Cp2Fe and Ar/O3 gas mixtures onto a cryogenically cooled CsI window produced a dark-green charge-transfer complex, Cp2Fe-O3, that photodecomposed upon red (λ ≥ 600 nm) and infrared (λ ≥ 1000 nm) irradiation but was stable to green or blue irradiation. Products of photodecomposition were characterized by FT-IR, oxygen-18 labeling, and DFT calculations using the B3LYP functionals and the 6-311G++(d,2p) basis set. Likely, photochemical products included four structures having the molecular formula C10H10FeO, identified by DFT calculations based on their calculated infrared spectra and (18)O isotope shifts. Each of these calculated molecules had one intact and fully coordinated η(5)-C5H5 cyclopentadienyl (Cp) ring and (1) an η(5)-C5H5O cyclic ether (pyran ring) (2b), (2) an η(4)-C5H5O linear aldehyde (2c), (3) a bidentate cyclic aldehyde with a seven-membered ring including the iron atom (2d), or (4) an Fe-O bond and an η(2)-C5H5 (Cp) ring (2e). No conclusive evidence for a gas-phase thermal reaction between ferrocene and ozone was observed under the conditions of these experiments. However, strong evidence for a surface-catalyzed thermal reaction was observed in merged-jet experiments wherein the gases were premixed before deposition. Surface-catalyzed ferrocene-ozone reaction products included a thin film of Fe2O3 observed on the walls of the merged tube as well as cyclopentadiene (C5H6), cyclopentadienone (C5H4O), and further oxidation products observed in the matrix. Possible mechanisms for both the photochemical and the thermal reactions are discussed.

Charge transfer complexes of metal-free phthalocyanine radical anions with decamethylmetallocenium cations: (Cp*2Co+)(H2Pc˙-)·solvent and (Cp*2Cr+)(H2Pc˙-)·4C6H4Cl2.

PubMed

Konarev, Dmitri V; Khasanov, Salavat S; Ishikawa, Manabu; Otsuka, Akihiro; Yamochi, Hideki; Saito, Gunzi; Lyubovskaya, Rimma N

2017-03-14

Charge transfer complexes (Cp* 2 Co + )(H 2 Pc˙ - )·0.5C 6 H 4 Cl 2 ·0.7C 6 H 5 CN·0.3C 6 H 14 (1) and (Cp* 2 Cr + )(H 2 Pc˙ - )·4C 6 H 4 Cl 2 (2) have been obtained as single crystals. Both complexes contain metal-free phthalocyanine (Pc) radical anions and decamethylmetallocenium cations. Reduction of the Pc macrocycle leads to the appearance of new bands at 1026-1030 nm in the NIR range and blue shifts of both Soret and Q-bands of H 2 Pc in the spectra of 1 and 2. The geometry of the Pc macrocycles supports the formation of H 2 Pc˙ - by the alternation of shorter and longer C-N(imine) bonds in the macrocycles in 2. Complex 1 contains pairs of H 2 Pc˙ - having effective π-π interactions with two sandwiched Cp* 2 Co + cations, whereas complex 2 contains stacks composed of alternating Cp* 2 Cr + and H 2 Pc˙ - ions. The magnetic moment of 1 is 1.64 μ B at 300 K due to the contribution of the H 2 Pc˙ - spins with the S = 1/2 state and diamagnetism of Cp* 2 Co + . This is supported by the observation of a narrow EPR signal of 1 with g = 2.0032-2.0036 characteristic of H 2 Pc˙ - . Strong antiferromagnetic coupling of spins with a Weiss temperature of -23 K is observed between H 2 Pc˙ - in 1. This coupling is probably mediated by the Cp* 2 Co + cations. The magnetic moment of 2 is 4.18 μ B at 300 K indicating the contribution of both paramagnetic H 2 Pc˙ - (S = 1/2) and Cp* 2 Cr + (S = 3/2) species. In spite of the presence of stacks of alternating ions in 2, only weak magnetic coupling is observed with a Weiss temperature of -4 K most probably due to ineffective π-π interactions between Cp* 2 Cr + and H 2 Pc˙ - . The EPR spectrum of 2 contains an asymmetric signal attributed to Cr III (g 1 = 3.9059-3.9220) and a narrow Lorentzian signal from H 2 Pc˙ - with g 2 = 1.9943-1.9961. In addition to these signals, a broad EPR signal grows in intensity below 80 K with g 4 = 2.1085-2.2438 which can be attributed to both paramagnetic Cp* 2 Cr + and H 2 Pc˙ - species having exchange interactions.

Endogenous and exogenous porphyrins as photosensitizers in the Hep-2 human carcinoma cell line.

PubMed

Alvarez, M G; Milanesio, M; Rivarola, V; Durantini, E; Batlle, A; Fukuda, H

2009-07-01

The photodynamic activity of three photosensitizers (PS): AL-induced PPIX, the porphyrin derivative 5-(4-trimethylammoniumphenyl)-10, 5, 20-tris (2,4,6- trimethoxyphenyl) porphyrin (CP) and the molecular dyad porphyrin-C(60) (P-C(60)), the last two incorporated into liposomal vesicles, was evaluated on Hep-2 human larynx carcinoma cell line. ALA-induced accumulation of the endogenous PS PPIX, reached saturation values between 5 and 24 h incubation time; the maximal PPIX content was 5.7 nmol/106 cells. The same intracellular level was accumulated when the cationic porphyrin CP was used, while the amount of P-C(60) attained was 1.5 nmol/106 cells. Under violet-blue exciting light, the fluorescence of PPIX and P-C(60) was found in the cytoplasm showing a granular appearance indicating lysosomal localization. CP was mainly detected as a filamentous pattern characteristic of mitochondrial localization. No dark cytotoxicity was observed using 1mM ALA, 5 microM CP and 1 microM P-C(60) after 24 h incubation. Cell morphology was analyzed using Hoechst-33258, toluidine blue staining, TUNEL assay and DNA fragmentation, 24 h after irradiation with 54 J/cm2. When photosensitized with ALA and P-C(60), chromatine condensation characteristic of apoptotic cell death was found; instead, 58 % of necrotic cells were observed with CP. The results show that in the Hep-2 cells, of the three PS analyzed, the molecular dyad P-C(60) was more efficient than CP and PPIX, and confirm that PDT can induce different mechanisms of cell death depending on the PS and the irradiation dose.

Regioselectivity in the gas-phase reactions of the O- radical anion with ([eta]5-cyclopentadienyl)tricarbonylmanganese(I) and ([eta]5-methylcyclopentadienyl)tricarbonylmanganese(I): formation and structure of C5H5MnO-n and C6H7MnO-n (n = 1, 2) ions

NASA Astrophysics Data System (ADS)

van den Berg, Klaas Jan; Ingemann, Steen; Nibbering, Nico M. M.

1994-06-01

The gas-phase reactions of the O- ion with ([eta]5-cyclopentadienyl)tricarbonylmanganese(I), CpMn(CO)3, and ([eta]5-methylcyclopentadienyl)tricarbonylmanganese(I), CH3CpMn(CO)3, have been studied with Fourier transform ion cyclotron resonance. The main reactions are (i) proton abstraction, (ii) loss of CO2, and (iii) expulsion of two or three CO molecules from the collision complex. Initial attack on a CO ligand is the main process as indicated by experiments with 18O- and the ion/molecule reactions of the product ions resulting from the loss of three CO molecules with water, aliphatic alcohols, methanethiol and SO2. The attack on a CO ligand followed by loss of three CO molecules is suggested to yield C5H5MnO- ions with a (cyclopentadienone)MnH- structure in the reaction with CpMn(CO)3 and (methylcyclopentadienone)MnH- ions if CH3CpMn(CO)3 is the substrate. A possible mechanism for the process leading to the indicated transformation of the Cp and CH3Cp ligands into C5H4O and CH3C5H3O ligands, respectively, is discussed together with the formation of (fulvene)Mn(OH)- ions following attack of O- on CH3CpMn(CO)3. The (cyclopentadienone)MnH- and (methylcyclopentadienone)MnH- ions react with N2O by oxygen atom abstraction to form C5H5MnO-2 and C6H7MnO-2 ions, respectively.

Prevalence of exocrine pancreatic insufficiency in patients with chronic pancreatitis without follow-up. PANCR-EVOL Study.

PubMed

Marra-Lopez Valenciano, Carlos; Bolado Concejo, Federico; Marín Serrano, Eva; Millastre Bocos, Judith; Martínez-Moneo, Emma; Pérez Rodríguez, Esperanza; Francisco González, María; Del Pozo-García, Andrés; Hernández Martín, Anaiansi; Labrador Barba, Elena; Orera Peña, María Luisa; de-Madaria, Enrique

2018-02-01

Exocrine pancreatic insufficiency (EPI) is an important complication of chronic pancreatitis (CP). Guidelines recommend to rule out EPI in CP, to detect those patients who would benefit from pancreatic enzyme replacement therapy. The aim of this study was to evaluate the prevalence of EPI in patients with CP without follow-up in the last 2 years and to describe their nutritional status and quality of life (QoL). This was a cross-sectional, multicenter Spanish study. CP patients without follow-up by a gastroenterologist or surgeon in at least 2 years were included. EPI was defined as fecal elastase test <200mcg/g. For nutritional assessment, laboratory and anthropometric data were obtained. QoL was investigated using the EORTC QLQ-C30 questionnaire. 64 patients (mean age 58.8±10.3 years, 85.9% men) from 10 centers were included. Median time since diagnosis of CP was 58.7 months [37.7-95.4]. Forty-one patients (64.1%) had EPI. Regarding nutritional status, the following differences were observed (EPI vs. Non-EPI): BMI (23.9±3.5kg/m 2 vs. 25.7±2.5, p=0.03); glucose (121 [96-189] mg/dL vs. 98 [90-116], p=0.006); HbA1c 6.6% [6.0-8.4] vs. 5.5 [5.3-6.0], p=0.0005); Vitamin A (0.44mg/L [0.35-0.57] vs. 0.53 [0.47-0.63], p=0.048) and Vitamin E (11.2±5.0μg/ml vs. 14.4±4.3, p=0.03). EPI group showed a worse EORTC QLQ-C30 score on physical (93.3 [66.7-100] vs. 100 [93.3-100], p=0.048) and cognitive function (100 [83.3-100] vs. 100 [100-100], p=0.04). Prevalence of EPI is high in patients with CP without follow-up. EPI group had higher levels of glucose, lower levels of vitamins A and E and worse QoL. Copyright © 2017 Elsevier España, S.L.U. All rights reserved.

Preparation, structure and some chemistry of FcC[identically equal to]CC[identically equal to]CC[identically equal to]CRu(dppe)Cp

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bruce, Michael I.; Humphrey, Paul A.; Jevric, Martyn

The synthesis of Fc(C{triple_bond}C){sub 3}Ru(dppe)Cp (2) from Fc(C{triple_bond}C){sub 3}SiMe{sub 3} and RuCl(dppe)Cp is described, together with its reactions with tcne to give the tetracyano-dienyl FcC{triple_bond}CC{triple_bond}C{l_brace}C[{triple_bond}C(CN){sub 2}]{r_brace}{sub 2}Ru(dppe)Cp (3) and -cyclobutenyl FcC{triple_bond}CC{triple_bond}C{l_brace}C{triple_bond}CC(CN){sub 2}C(CN){sub 2}{r_brace}Ru(dppe)Cp (4), with Co{sub 2}({mu}-dppm){sub n}(CO){sub 8-2n} (n = 0, 1) to give FcC{sub 2}{l_brace}Co{sub 2}(CO){sub 6}{r_brace}C{sub 2}{l_brace}Co{sub 2}(CO){sub 6}{r_brace}CCRu(dppe)Cp (5) and FcC{triple_bond}CC{triple_bond}CC{sub 2}{l_brace}Co{sub 2}({mu}-dppm)(CO){sub 4}{r_brace}Ru(dppe)Cp (6), respectively, and with Os{sub 3}(CO){sub 10}(NCMe){sub 2} to give Os{sub 3}{l_brace}{mu}{sub 3}-C{sub 2}C{triple_bond}CC{triple_bond}C[Ru(dppe)Cp]{r_brace}(CO){sub 10} (7). On standing in solution, the latter isomerises to the cyclo-metallated derivative Os{sub 3}({mu}-H){l_brace}{mu}{sub 3}-C[Ru(dppe)Cp]CCC[({eta}-C{sub 5}H{sub 3})FeCp]{r_brace}(CO){sub 8} (8). X-ray structural determinations of 1, 2, 6 andmore » 7 are reported.« less

Diverse Reactivity of ECp* (E = Al, Ga) toward Low-Coordinate Transition Metal Amides [TM(N(SiMe3)2)2] (TM = Fe, Co, Zn): Insertion, Cp* Transfer, and Orthometalation.

PubMed

Weßing, Jana; Göbel, Christoph; Weber, Birgit; Gemel, Christian; Fischer, Roland A

2017-03-20

The reactivity of the carbenoid group 13 metal ligands ECp* (E = Al, Ga) toward low valent transition metal complexes [TM(btsa) 2 ] (TM = Fe, Co, Zn; btsa = bis(trimethylsilyl)amide) was investigated, revealing entirely different reaction patterns for E = Al and Ga. Treatment of [Co(btsa) 2 ] with AlCp* yields [Cp*Co(μ-H)(Al(κ 2 -(CH 2 SiMe 2 )NSiMe 3 )(btsa))] (1) featuring an unusual heterometallic bicyclic structure that results from the insertion of AlCp* into the TM-N bond with concomitant ligand rearrangement including C-H activation at one amide ligand. For [Fe(btsa) 2 ], complete ligand exchange gives FeCp* 2 , irrespective of the employed stoichiometric ratio of the reactants. In contrast, treatment of [TM(btsa) 2 ] (TM = Fe, Co) with GaCp* forms the 1:1 and 1:2 adducts [(GaCp*)Co(btsa) 2 ] (2) and [(GaCp*) 2 Fe(btsa) 2 ] (3), respectively. The tendency of AlCp* to undergo Cp* transfer to the TM center appears to be dependent on the nature of the TM center: For [Zn(btsa) 2 ], no Cp* transfer is observed on reaction with AlCp*; instead, the insertion product [Zn(Al(η 2 -Cp*)(btsa)) 2 ] (4) is formed. In the reaction of [Co(btsa) 2 ] with the trivalent [Cp*AlH 2 ], transfer of the amide ligands without further ligand rearrangement is observed, leading to [Co(μ-H) 4 (Al(η 2 -Cp*)(btsa)) 2 ] (5).

Cytotect®CP as salvage therapy in patients with CMV infection following allogeneic hematopoietic cell transplantation: a multicenter retrospective study.

PubMed

Alsuliman, Tamim; Kitel, Caroline; Dulery, Rémy; Guillaume, Thierry; Larosa, Fabrice; Cornillon, Jérôme; Labussière-Wallet, Helene; Médiavilla, Clémence; Belaiche, Stéphanie; Delage, Jeremy; Alain, Sophie; Yakoub-Agha, Ibrahim

2018-04-13

Cytomegalovirus is one of the main contributing factors to high mortality rates in patients undergoing allogeneic hematopoietic cell transplantation (allo-HCT). The main factors of treatment failure are both drug resistance and intolerance. In some cases, Cytotect®CP CMV-hyperimmune globulin is used as salvage therapy. This study aims to investigate the safety and efficacy of Cytotect®CP as a salvage therapy in patients with CMV infection after allo-HCT. Twenty-three consecutive patients received Cytotect®CP for CMV infection after prior CMV therapy. At the time of Cytotect®CP introduction, 17 patients (74%) had developed acute GVHD and 15 patients (64%) were receiving steroid treatment; Cytotect®CP was used as monotherapy (n = 7) and in combination (n = 16). Overall, response was observed in 18 patients (78%) with a median time of 15 days (range: 3-51). Of the 18 responders, 4 experienced CMV reactivation, while 5 responders died within 100 days of beginning treatment. Of these 5 deaths, 4 were due to causes unrelated to CMV. Estimated 100-day OS from the introduction of Cytotect®CP was 69.6%. No statistically significant difference was observed in 100-day OS between responders and non-responders (73.7% vs 50.0%, p = 0.258). Cytotect®CP as salvage therapy is effective and well-tolerated. Given its safety profile, early treatment use should be considered.

Effects of clinical pathway implementation on antibiotic prescriptions for pediatric community-acquired pneumonia

PubMed Central

Zingarella, Silvia; Gastaldi, Andrea; Lundin, Rebecca; Perilongo, Giorgio; Frigo, Anna Chiara; Hamdy, Rana F.; Zaoutis, Theoklis; Da Dalt, Liviana; Giaquinto, Carlo

2018-01-01

Background Italian pediatric antimicrobial prescription rates are among the highest in Europe. As a first step in an Antimicrobial Stewardship Program, we implemented a Clinical Pathway (CP) for Community Acquired Pneumonia with the aim of decreasing overall prescription of antibiotics, especially broad-spectrum. Materials and methods The CP was implemented on 10/01/2015. We collected antibiotic prescribing and outcomes data from children aged 3 months-15 years diagnosed with CAP from 10/15/2014 to 04/15/2015 (pre-intervention period) and from 10/15/2015 to 04/15/2016 (post-intervention period). We assessed antibiotic prescription differences pre- and post-CP, including rates, breadth of spectrum, and duration of therapy. We also compared length of hospital stay for inpatients and treatment failure for inpatients and outpatients. Chi-square and Fisher’s exact test were used to compare categorical variables and Wilcoxon rank sum test was used to compare quantitative outcomes. Results 120 pre- and 86 post-intervention clinic visits were identified with a diagnosis of CAP. In outpatients, we observed a decrease in broad-spectrum regimens (50% pre-CP vs. 26.8% post-CP, p = 0.02), in particular macrolides, and an increase in narrow-spectrum (amoxicillin) post-CP. Post-CP children received fewer antibiotic courses (median DOT from 10 pre-CP to 8 post-CP, p<0.0001) for fewer days (median LOT from 10 pre-CP to 8 post-CP, p<0.0001) than their pre-CP counterparts. Physicians prescribed narrow-spectrum monotherapy more frequently than broad-spectrum combination therapy (DOT/LOT ratio 1.157 pre-CP vs. 1.065 post-CP). No difference in treatment failure was reported before and after implementation (2.3% pre-CP vs. 11.8% post-CP, p = 0.29). Among inpatients we also noted a decrease in broad-spectrum regimens (100% pre-CP vs. 66.7% post-CP, p = 0.02) and the introduction of narrow-spectrum regimens (0% pre-CP vs. 33.3% post-CP, p = 0.02) post-CP. Hospitalized patients received fewer antibiotic courses post-CP (median DOT from 18.5 pre-CP to 10 post-CP, p = 0.004), while there was no statistical difference in length of therapy (median LOT from 11 pre-CP to 10 post-CP, p = 0.06). Days of broad spectrum therapy were notably lower post-CP (median bsDOT from 17 pre-CP to 4.5 post-CP, p <0.0001). No difference in treatment failure was reported before and after CP implementation (16.7% pre-CP vs. 15.4% post-CP, p = 1). Conclusions Introduction of a CP for CAP in a Pediatric Emergency Department led to reduction of broad-spectrum antibiotic prescriptions, of combination therapy and of duration of treatment both for outpatients and inpatients. PMID:29489898

Overview on the investigations of transgenic plums in Romania

USDA-ARS?s Scientific Manuscript database

Transgenic plums of Prunus domestica L. transformed with the Plum pox virus coat protein gene (PPV-CP) were the subjects of three experiments undertaken in Romania. In the first experiment, PPV-CP transgenic clones C2, C3, C4, C5, C6, PT3 and PT5 were evaluated for Sharka resistance under high natu...

Nutritional and endocrinologic evaluation of patients with craniopharyngioma.

PubMed

Nogueira, Mônica Cristina; Berbel Júnior, Alfredo Sérgio; Koenigkam-Santos, Marcel; Moreira, Ayrton Custódio; Nonino, Carla Barbosa; de Castro, Margaret

2015-12-01

Lesions of hypothalamus or adjacent brain structures by the craniopharyngioma (CP) and/or its treatment, as well as changes in orexigenic and anorexigenic hormones, are possible pathogenic factors for the obesity observed in CP patients. This study assessed anthropometric measurements, food intake, and biochemical markers of CP patients. Weight, height, skinfold thicknesses, circumferences, body composition, food intake evaluation, basal glucose, lipids, insulin, ghrelin, PYY, and HOMA-IR calculation were obtained from CP children (n = 10, 4F, aged 12 ± 4.2yr) and CP adults (n = 27,13F aged 42 ± 13 yr) and from 32 gender and age matched controls. Overweight/obesity was observed in 51.4% of the patients at the diagnosis and increased to 86.5% at the time of the study. Obesity was more frequent in patients with grade 2 hypothalamic involvement. Most anthropometric measurements were similar in patients and controls. Caloric intake was lower in CP adults, without difference between children. Lipid intake was higher in CP patients. Carbohydrate and protein intakes were lower in CP children, with no difference between adult groups. There were no differences in micronutrients intake as well as in insulin and PYY levels, and HOMA-IR between patients and controls. HDL-c was lower in CP adults and ghrelin higher in CP children. There is a high rate of overweight/obesity in CP patients at the diagnosis and throughout the follow-up period. Obesity was associated with degree of hypothalamic involvement but not with caloric intake. Obesity and a lipid rich diet may have contributed to the dyslipidemia observed in CP patients. Copyright © 2015 European Society for Clinical Nutrition and Metabolism. Published by Elsevier Ltd. All rights reserved.

Base free N-alkylation of anilines with ArCH2OH and transfer hydrogenation of aldehydes/ketones catalyzed by the complexes of η5-Cp*Ir(iii) with chalcogenated Schiff bases of anthracene-9-carbaldehyde.

PubMed

Dubey, Pooja; Gupta, Sonu; Singh, Ajai K

2018-03-12

The condensation of anthracene-9-carbaldehyde with 2-(phenylthio/seleno)ethylamine results in Schiff bases [PhS(CH 2 ) 2 C[double bond, length as m-dash]N-9-C 14 H 9 ](L1) and [PhSe(CH 2 ) 2 C[double bond, length as m-dash]N-9-C 14 H 9 ] (L2). On their reaction with [(η 5 -Cp*)IrCl(μ-Cl)] 2 and CH 3 COONa at 50 °C followed by treatment with NH 4 PF 6 , iridacycles, [(η 5 -Cp*)Ir(L-H)][PF 6 ] (1: L = L1; 2: L = L2), result. The same reaction in the absence of CH 3 COONa gives complexes [(η 5 -Cp*)Ir(L)Cl][PF 6 ] (3-4) in which L = L1(3)/L2(4) ligates in a bidentate mode. The ligands and complexes were authenticated with HR-MS and NMR spectra [ 1 H, 13 C{ 1 H} and 77 Se{ 1 H} (in the case of L2 and its complexes only)]. Single crystal structures of L2 and half sandwich complexes 1-4 were established with X-ray crystallography. Three coordination sites of Ir in each complex are covered with η 5 -Cp* and on the remaining three, donor atoms present are: N, S/Se and C - /Cl - , resulting in a piano-stool structure. The moisture and air insensitive 1-4 act as efficient catalysts under mild conditions for base free N-alkylation of amines with benzyl alcohols and transfer hydrogenation (TH) of aldehydes/ketones. The optimum loading of 1-4 as a catalyst is 0.1-0.5 mol% for both the activations. The best reaction temperature is 80 °C for transfer hydrogenation and 100 °C for N-alkylation. The mercury poisoning test supports a homogeneous pathway for both the reactions catalyzed by 1-4. The two catalytic processes are most efficient with 3 followed by 4 > 1 > 2. The mechanism proposed on the basis of HR-MS of the reaction mixtures of the two catalytic processes taken after 1-2 h involves the formation of an alkoxy and hydrido species. The real catalytic species proposed in the case of iridacycles results due to the loss of the Cp* ring.

Biodistribution and radiation dosimetry of 18F-CP-18, a potential apoptosis imaging agent, as determined from PET/CT scans in healthy volunteers.

PubMed

Doss, Mohan; Kolb, Hartmuth C; Walsh, Joseph C; Mocharla, Vani; Fan, Hong; Chaudhary, Ashok; Zhu, Zhihong; Alpaugh, R Katherine; Lango, Miriam N; Yu, Jian Q

2013-12-01

(18)F-CP-18, or (18S,21S,24S,27S,30S)-27-(2-carboxyethyl)-21-(carboxymethyl)-30-((2S,3R,4R,5R,6S)-6-((2-(4-(3-F18-fluoropropyl)-1H-1,2,3-triazol-1-yl)acetamido)methyl)-3,4,5-trihydroxytetrahydro-2H-pyran-2-carboxamido)-24-isopropyl-18-methyl-17,20,23,26,29-pentaoxo-4,7,10,13-tetraoxa-16,19,22,25,28-pentaazadotriacontane-1,32-dioic acid, is being evaluated as a tissue apoptosis marker for PET imaging. The purpose of this study was to determine the biodistribution and estimate the normal-organ radiation-absorbed doses and effective dose from (18)F-CP-18. Successive whole-body PET/CT scans were obtained at approximately 7, 45, 90, 130, and 170 min after intravenous injection of (18)F-CP-18 in 7 healthy human volunteers. Blood samples and urine were collected between the PET/CT scans, and the biostability of (18)F-CP-18 was assessed using high-performance liquid chromatography. The PET scans were analyzed to determine the radiotracer uptake in different organs. OLINDA/EXM software was used to calculate human radiation doses based on the biodistribution of the tracer. (18)F-CP-18 was 54% intact in human blood at 135 min after injection. The tracer cleared rapidly from the blood pool with a half-life of approximately 30 min. Relatively high (18)F-CP-18 uptake was observed in the kidneys and bladder, with diffuse uptake in the liver and heart. The mean standardized uptake values (SUVs) in the bladder, kidneys, heart, and liver at around 50 min after injection were approximately 65, 6, 1.5, and 1.5, respectively. The calculated effective dose was 38 ± 4 μSv/MBq, with the urinary bladder wall having the highest absorbed dose at 536 ± 61 μGy/MBq using a 4.8-h bladder-voiding interval for the male phantom. For a 1-h voiding interval, these doses were reduced to 15 ± 2 μSv/MBq and 142 ± 15 μGy/MBq, respectively. For a typical injected activity of 555 MBq, the effective dose would be 21.1 ± 2.2 mSv for the 4.8-h interval, reduced to 8.3 ± 1.1 mSv for the 1-h interval. (18)F-CP-18 cleared rapidly through the renal system. The urinary bladder wall received the highest radiation dose and was deemed the critical organ. Both the effective dose and the bladder dose can be reduced by frequent voiding. From the radiation dosimetry perspective, the apoptosis imaging agent (18)F-CP-18 is suitable for human use.

Comparison of inter-trial recovery times for the determination of critical power and W' in cycling.

PubMed

Karsten, Bettina; Hopker, James; Jobson, Simon A; Baker, Jonathan; Petrigna, Luca; Klose, Andreas; Beedie, Christopher

2017-07-01

Critical Power (CP) and W' are often determined using multi-day testing protocols. To investigate this cumbersome testing method, the purpose of this study was to compare the differences between the conventional use of a 24-h inter-trial recovery time with those of 3 h and 30 min for the determination of CP and W'. 9 moderately trained cyclists performed an incremental test to exhaustion to establish the power output associated with the maximum oxygen uptake (p[Formula: see text] max ), and 3 protocols requiring time-to-exhaustion trials at a constant work-rate performed at 80%, 100% and 105% of p[Formula: see text] max. Design: Protocol A utilised 24-h inter-trial recovery (CP 24 /W' 24 ), protocol B utilised 3-h inter-trial recovery (CP 3 /W' 3 ), and protocol C used 30-min inter-trial recovery period (CP 0.5 /W' 0.5 ). CP and W' were calculated using the inverse time (1/t) versus power (P) relation (P = W'(1/t) + CP). 95% Limits of Agreement between protocol A and B were -9 to 15 W; -7.4 to 7.8 kJ (CP/W') and between protocol A and protocol C they were -27 to 22 W; -7.2 to 15.1 kJ (CP/W'). Compared to criterion protocol A, the average prediction error of protocol B was 2.5% (CP) and 25.6% (W'), whilst for protocol C it was 3.7% (CP) and 32.9% (W'). 3-h and 30-min inter-trial recovery time protocols provide valid methods of determining CP but not W' in cycling.

Restoration of prostaglandin E2-producing splenic macrophages in sup 89 Sr-treated mice with bone marrow from Corynebacterium parvum primed donors

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shibata, Y.

1989-05-01

Administration of Corynebacterium parvum (CP), 56 mg/kg ip to CBA/J mice effected the induction of prostaglandin E2 (PGE2) producing macrophages (M phi) in the bone marrow and the spleen. Maximal release of PGE2 from M phi cultured in vitro with calcium ionophore A23187 for 2 h was reached by marrow M phi removed on 5 days after CP (450 ng/mg cell protein), and by splenic M phi 9 days after CP (400 ng/mg). Neither M phi population, however, yielded more than 6.0 ng/mg leukotriene C4. To assess ontogenic relationships mice were depleted of bone marrow and blood monocytes by ivmore » injection of the bone-seeking isotope, 89Sr. CP was given at several points before or after bone marrow cell depletion. PGE2 production by splenic M phi harvested on day 9 after CP was profoundly impaired when CP was administered either concurrently with or 3 days after 89Sr. When CP was administered 1, 3, 5, and 7 days before 89Sr, however, the induction of PGE2-producing M phi in the spleen was unaffected. To determine whether bone marrow cells from CP-injected donors can restore PGE2-producing splenic M phi (PGSM) in 89Sr-mice, recipient mice which had and had not received CP 3 days after 89Sr were transfused with 5 x 10(6) syngeneic bone marrow cells from donor mice prepared at varying intervals after CP administration. The results clearly indicate the capacity of bone marrow cells harvested on either day 1 or 2 following CP to restore PGSM in CP-primed, but not unprimed, recipients.« less

Open-Shell Lanthanide(II+) or -(III+) Complexes Bearing σ-Silyl and Silylene Ligands: Synthesis, Structure, and Bonding Analysis

PubMed Central

2015-01-01

Complexes featuring lanthanide (Ln)–Si bonds represent a highly neglected research area. Herein, we report a series of open-shell LnII+ and LnIII+ complexes bearing σ-bonded silyl and base-stabilized N-heterocyclic silylene (NHSi) ligands. The reactions of the LnIII+ complexes Cp3Ln (Ln = Tm, Ho, Tb, Gd; Cp = cyclopentadienide) with the 18-crown-6 (18-cr-6)-stabilized 1,4-oligosilanyl dianion [(18-cr-6)KSi(SiMe3)2SiMe2SiMe2Si(SiMe3)2K(18-cr-6)] (1) selectively afford the corresponding metallacyclopentasilane salts [Cp2Ln({Si(SiMe3)2SiMe2}2)]−[K2(18-cr-6)2Cp]+ [Ln = Tm (2a), Ho (2b), Tb (2c), Gd (2d)]. Complexes 2a–2d represent the first examples of structurally characterized Tm, Ho, Tb, and Gd complexes featuring Ln–Si bonds. Strikingly, the analogous reaction of 1 with the lighter element analogue Cp3Ce affords the acyclic product [Cp3CeSi(SiMe3)2SiMe2SiMe2Si(SiMe3)2-Cp3Ce]2–2[K(18-cr-6)]+ (3) as the first example of a complex featuring a Ce–Si bond. In an alternative synthetic approach, the aryloxy-functionalized benzamidinato NHSi ligand Si(OC6H4-2-tBu){(NtBu)2CPh} (4a) and the alkoxy analogue Si(OtBu){(NtBu)2CPh} (4b) were reacted with Cp*2Sm(OEt2), affording, by OEt2 elimination, the corresponding silylene complexes, both featuring SmII+ centers: Cp*2Sm ← :Si(O–C6H4-2-tBu){(NtBu)2CPh} (6) and Cp*2Sm ← :Si(OtBu){(NtBu)2CPh} (5). Complexes 5 and 6 are the first four-coordinate silylene complexes of any f-block element to date. All complexes were fully characterized by spectroscopic means and by single-crystal X-ray diffraction analysis. In the series 2a–2d, a linear correlation was observed between the Ln–Si bond lengths and the covalent radii of the corresponding Ln metals. Moreover, in complexes 5 and 6, notably long Sm–Si bonds are observed, in accordance with a donor–acceptor interaction between Si and Sm [5, 3.4396(15) Å; 6, 3.3142(18) Å]. Density functional theory calculations were carried out for complexes 2a–2d, 5, and 6 to elucidate the bonding situation between the LnII+ or LnIII+ centers and Si. In particular, a decrease in the Mayer bond order (MBO) of the Ln–Si bond is observed in the series 2a–2d in moving from the lighter to the heavier lanthanides (Tm = 0.53, Ho = 0.62, Tb = 0.65, and Gd = 0.75), which might indicate decreasing covalency in the Ln–Si bond. In accordance with the long bond lengths observed experimentally in complexes 5 and 6, comparatively low MBOs were determined for both silylene complexes (5, 0.24; 6, 0.25) . PMID:25756230

DOE Office of Scientific and Technical Information (OSTI.GOV)

Abugideiri, F.; Kelland, M.A.; Poli, R.

Cp*MoH[sub 5](PMe[sub 3]) has been prepared from Cp*MoCl[sub 2](PMe[sub 3]) and LiAlH[sub 4]. The compound is analogous to the previously reported Cp*WH[sub 5](PMe[sub 3]) and CpWH[sub 5](PMe[sub 3]) (Green, M.L.H.; Parkin, G.J. Chem. Soc., Chem. Commun. 1984, 1467. Schrock, R. R.; et al. Organometallics 1986, 5, 1681) for which structural assignments were not made. A single sharp [sup 1]H-NMR resonance is observed for the five hydrides down to 183 K, consistent with either a static symmetric structure or a highly fluxional structure, either classical or nonclassical. The measured minimum longtudinal relaxation time, T[sub 1], is quite long (780 ms atmore » 400 MHz and 230 K) and consistent with a classical structure based on the pentagonal bipyramid which gives rise to a substantially anisotropic moment of inertia. 14 refs., 1 tab.« less

Maternal ambient air pollution exposure preconception and during early gestation and offspring congenital orofacial defects

PubMed Central

Zhu, Yeyi; Zhang, Cuilin; Liu, Danping; Grantz, Katherine L.; Wallace, Maeve; Mendola, Pauline

2015-01-01

Background Maternal air pollution exposure has been related to orofacial clefts but the literature is equivocal. Potential chronic preconception effects have not been studied. Objectives Criteria air pollutant exposure during three months preconception and gestational weeks 3–8 was studied in relation to orofacial defects. Methods Among 188,102 live births and fetal deaths from the Consortium on Safe Labor (2002–2008), 63 had isolated cleft palate (CP) and 159 had isolated cleft lip with or without cleft palate (CL ± CP). Exposures were estimated using a modified Community Multiscale Air Quality model. Logistic regression with generalized estimating equations adjusted for site/region and maternal demographic, lifestyle and clinical factors calculated the odds ratio (OR) and 95% CI per interquartile increase in each pollutant. Results Preconception, carbon monoxide (CO; OR = 2.24; CI: 1.21, 4.16) and particulate matter (PM) ≤10 μm (OR = 1.72; CI: 1.12, 2.66) were significantly associated with CP, while sulfur dioxide (SO2) was associated with CL ± CP (OR = 1.93; CI: 1.16, 3.21). During gestational weeks 3–8, CO remained a significant risk for CP (OR = 2.74; CI: 1.62, 4.62) and nitrogen oxides (NOx; OR = 3.64; CI: 1.73, 7.66) and PM ≤2.5 μm (PM2.5; OR = 1.74; CI: 1.15, 2.64) were also related to the risk. Analyses by individual week revealed that positive associations of NOx and PM2.5 with CP were most prominent from weeks 3–6 and 3–5, respectively. Conclusions Exposure to several criteria air pollutants preconception and during early gestation was associated with elevated odds for CP, while CL ± CP was only associated with preconception SO2 exposure. PMID:26099933

Dietary protein quality and quantity affect lactational responses to corn distillers grains: a meta-analysis.

PubMed

Hollmann, M; Allen, M S; Beede, D K

2011-04-01

Diet fermentability influences lactational responses to feeding corn distillers grains (CDG) to dairy cows. However, some measures of diet fermentability are inherently related to the concentration and characteristics of corn-based ingredients in the ration. Corn-based feeds have poor protein quality, unable to meet the essential AA requirements of lactating cows. We conducted a meta-analysis of treatment means (n=44) from the scientific literature to evaluate responses in milk yield (MY) and milk true protein concentration and yield to dietary CDG. The test variable was the difference in response between the CDG diet mean and the control diet mean (0% CDG) within experiment. Fixed variables were CDG concentration of the diet [% of dietary dry matter (DM)] and crude protein (CP) concentration and fractions of CP based on origin (corn-based versus non-corn-based feeds) of control and CDG diets. Diets with CDG ranged from 4 to 42% CDG, DM basis. Non-corn-based dietary CP averaged 6.3±3.32% of total DM. Milk yield and milk true protein yield responses to added CDG were maximized when approximately 8.5% of the total dietary DM was non-corn-based CP. Milk yield response peaked for higher-producing cows (>30.0 kg MY/cow per day) at 4.3% dietary corn-based CP, but decreased linearly for lower-producing cows (<30.0 kg MY/cow per day) as corn-based dietary CP increased. Milk true protein yield response decreased as corn-based dietary CP concentration increased but milk true protein concentration response was not decreased when CDG diets had more than 6.5% dietary non-corn-based CP. Overall, 8.5% dietary non-corn-based CP was necessary in lactation diets to maximize lactational responses to dietary CDG. The necessity of dietary non-corn-based CP to maximize milk and milk protein yields limits the amount of dietary corn-based CP, including that from CDG, which can be included in rations without overfeeding N. Copyright © 2011 American Dairy Science Association. Published by Elsevier Inc. All rights reserved.

Reducing crude protein and rumen degradable protein with a constant concentration of rumen undegradable protein in the diet of dairy cows: Production performance, nutrient digestibility, nitrogen efficiency, and blood metabolites.

PubMed

Bahrami-Yekdangi, M; Ghorbani, G R; Khorvash, M; Khan, M A; Ghaffari, M H

2016-02-01

The goals of ruminant protein nutrition are to provide adequate amounts of RDP for optimal ruminal efficiency and to obtain the desired animal productivity with a minimum amount of dietary CP. The aim of the present study was to examine effects of decreasing dietary protein by decreasing RDP with the optimum concentration of RUP on production performance, nutrient digestibility, N retention, rumen fermentation parameters, and blood metabolites in high-producing Holstein cows in early lactation. Nine multiparous lactating cows (second parities, averaging 50 ± 12 d in milk and milk yield of 48 ± 5 kg/d) were used in a triplicate 3 × 3 Latin square design with 3 rations: 1) a total mixed ration (TMR) containing 16.4% CP (10.9% RDP based on DM), 2) a TMR containing 15.6% CP (10% RDP), and 3) a TMR containing 14.8% CP (9.3% RDP). The level of RUP was constant at 5.5% DM across the treatments. All diets were calculated to supply a postruminal lysine to methionine ratio of about 3:1. Dry matter intake, milk yield and composition, 4% fat-corrected milk, and energy-corrected milk were not significantly affected by decreasing dietary CP and RDP levels. Cows fed 16.4% CP diets had greater ( < 0.01) CP and RDP intakes, which resulted in a trend toward greater concentrations of plasma urea N compared with other treatments. Daily N intake linearly decreased ( < 0.01) with decreasing dietary CP and RDP levels, whereas the intake of RUP and fecal N excretion (g/d) did not change. Apparent digestibility of nutrients, ruminal pH, and NH-N concentration were not affected with decreasing dietary CP and RDP levels. Apparent N efficiency increased, and RDP N intake and predicted urine N output decreased with decreased concentration of dietary CP and RDP in the diets ( < 0.01). Blood metabolites were not affected by treatments. In conclusion, to improve the efficiency of N utilization by early-lactation dairy cows, 9.3% RDP in rations provides adequate protein to optimize milk production while minimizing N excretion in urine when the amounts of lysine and methionine and the lysine to methionine ratio are balanced with sufficient dietary RUP.

The protective effect of infliximab on cisplatin-induced intestinal tissue toxicity.

PubMed

Aydin, I; Kalkan, Y; Ozer, E; Yucel, A F; Pergel, A; Cure, E; Cure, M C; Sahin, D A

2014-01-01

Cisplatin (CP) is a popular chemotherapeutic agent. However, high doses of CP may lead to severe side effects to the gastrointestinal system. The aim of this study was to investigate the protective effects of infliximab on small intestine injury induced by high doses of CP. The A total of 30 rats were equally divided into three groups, including sham (C), cisplatin (CP), and cisplatin + infliximab (CPI). The CP group was treated with 7 mg/kg intraperitoneal cisplatin, and a laparotomy was performed 5 days later. The CPI group received 7 mg/kg infliximab intraperitoneally, were administered 7 mg/kg cisplatin 4 days later, and a laparotomy was performed 5 days after receiving cisplatin. Histopathological and immunohistochemical analysis of small intestine tissue sections were performed, and superoxide dismutase, malondialdehyde, and TNF-α levels were measured. Histopathological evaluation revealed that the CP group had damage in the epithelium and connective tissue, but this damage was significantly improved in the CPI group (p < 0.05). In addition, these histopathological findings were confirmed by biochemical analyses. These results suggest that infliximab is protective against the adverse effects of CP.

Recombinant glucose uptake system

DOEpatents

Ingrahm, Lonnie O.; Snoep, Jacob L.; Arfman, Nico

1997-01-01

Recombinant organisms are disclosed that contain a pathway for glucose uptake other than the pathway normally utilized by the host cell. In particular, the host cell is one in which glucose transport into the cell normally is coupled to PEP production. This host cell is transformed so that it uses an alternative pathway for glucose transport that is not coupled to PEP production. In a preferred embodiment, the host cell is a bacterium other than Z. mobilis that has been transformed to contain the glf and glk genes of Z. mobilis. By uncoupling glucose transport into the cell from PEP utilization, more PEP is produced for synthesis of products of commercial importance from a given quantity of biomass supplied to the host cells.

Novel genotype of Tritrichomonas foetus from cattle in Southern Africa.

PubMed

Casteriano, Andrea; Molini, Umberto; Kandjumbwa, Kornelia; Khaiseb, Siegfried; Frey, Caroline F; Šlapeta, Jan

2016-12-01

Bovine trichomonosis caused by Tritrichomonas foetus is a significant reproductive disease of cattle. Preputial samples were collected using sheath washing technique in bulls in Namibia. Thirty-six trichomonad cultures were characterized using the TaqMan-probe commercial real-time polymerase chain reaction (PCR) diagnostic assay (VetMAX™-Gold Trich Detection Kit) and CYBR real-time PCR assay based on TFR3/4 primers. Diagnostic real-time PCRs and DNA sequencing of the internal transcribed region confirmed presence of T. foetus in 35 out of 36 samples. Multilocus genotyping using cysteine proteases (CP1, CP2, CP4, CP5, CP6, CP7, CP8, CP9) and malate dehydrogenase (MDH1) gene sequences demonstrate that the T. foetus in Namibia are genetically distinct from those characterized elsewhere. We report the discovery of a novel genotype of T. foetus in Namibian cattle, distinct from other T. foetus genotypes in Europe, South and North America and Australia. We suggest recognition of a 'Southern African' genotype of T. foetus. Identification of the new genotype of T. foetus demonstrates the need for wider global sampling to fully understand the diversity and origin of T. foetus causing disease in cattle or cats.

Bioconversion of Straw into Improved Fodder: Preliminary Treatment of Rice Straw Using Mechanical, Chemical and/or Gamma Irradiation

PubMed Central

2006-01-01

Crude protein (CP) content of mechanically ground rice straw into small particles by an electric grinder and reducing value (RV) and soluble protein (SP) in the culture filtrate were lower than that of the chopped straw into 5~6 cm lengths when both ground and chopped straws were fermented with Aspergillus ochraceus, A. terreus or Trichoderma koningii, at steady conditions. The reduction rate of RV, SP and CP was 22.2, 2.4, 7.3%; 9.1, 4.9, 8.5% or 0.0, 0.0, 3.6% for the three fungi, respectively. Chemical pretreatment of straw by soaking in NH4OH for a day caused significant increase in CP of the fermented straw than the other alkali and acidic pretreatments. Gamma irradiation pretreatment of dry and wet straw with water, specially at higher doses, 100, 200 or 500 kGy, caused significant increase in RV and SP as CP in the fermented straw by any of these fungi. Chemical-physical combination pretreatment of rice straw reduced the applied dose of gamma irradiation required for increasing fermentable ability of fungi from 500 kGy to 10 kGy with approximately the same results. Significant increases in RV and SP of fermented straw generally occurred as the dose of gamma irradiation for pretreated straw, which combined with NH4OH, gradually rose. Whereas, the increase percentage in CP of fermented straw that was pretreated by NH4OH-10 kGy was 12.4%, 15.4% or 8.6% for A. ochraceus, A. terreus or T. koningii, respectively. PMID:24039464

Effects of the [OC6F5] moiety upon structural geometry: crystal structures of half-sandwich tantalum(V) aryloxide complexes from reaction of Cp*Ta(N(t)Bu)(CH2R)2 with pentafluorophenol.

PubMed

Cole, Jacqueline M; Chan, Michael C W; Gibson, Vernon C; Howard, Judith A K

2011-10-01

The synthesis, chemical and structural characterization of a series of pentamethylcyclopentadienyl (Cp*) tantalum imido complexes and aryloxide derivatives are presented. Specifically, the imido complexes Cp*Ta(N(t)Bu)(CH(2)R)(2), where R = Ph [dibenzyl(tert-butylamido) (η(5)-pentamethylcyclopentadienyl)tantalum(IV) (1)], Me(2)Ph [tert-butylamido)bis(2-methyl-2-phenylpropyl) (η(5)-pentamethylcyclopentadienyl)tantalum(IV) (2)], CMe(3) [(tert-butylamido)bis(2,2-dimethylpropyl) (η(5)-pentamethylcyclopentadienyl)tantalum(IV) (3)], are reported. The crystal structure of (3) reveals α-agostic interactions with the Ta atom. The resulting increase in the tantalum core coordination improves electronic stability. As such it does not react with pentafluorophenol, in contrast to the other two reported imido complexes [(1) and (2)]. Addition of C(6)F(5)OH to (1) yields a dimeric aryl-oxide derivative, [Cp*Ta(CH(2)Ph)(OC(6)H(5))(μ-O)](2) [di-μ-oxido-bis[benzyl(pentafluorophenolato) (η(5)-pentamethylcyclopentadienyl)tantalum(V)] (4)]. Its crystal structure reveals long Ta-O(C(6)H(5)) bonds but short oxo-bridging Ta-O bonds. This is explained by accounting for the fierce electronic competition for the vacant d(π) orbitals of the electrophilic Ta(V) centre. Steric congestion around each metal is alleviated by a large twist angle (77.1°) between the benzyl and pentafluorophenyl ligands and the ordering of each of these groups into stacked pairs. The imido complex (2) reacts with C(6)F(5)OH to produce a mixture of Cp*Ta(OC(6)F(5))(4) [tetrakis(pentafluorophenolato)(η(5)-pentamethylcyclopentadienyl)tantalum(V) (5)] and [Cp*Ta(OC(6)F(5))(2)(μ-O)](2) [di-μ-oxido-bis[bis(pentafluorophenolato)(η(5)-pentamethylcyclopentadienyl)tantalum(V)] (6)]. Steric congestion is offset in both cases by the twisting of its pentafluorophenyl ligands. Particularly strong electronic competition for the empty d(π) metal orbitals in (6) is reflected in its bond geometry, and owes itself to the more numerous electron-withdrawing pentafluorophenyl ligands. The balance of steric and electronic factors affecting the reactivity of Cp* tantalum imido based complexes with pentafluorophenol is therefore addressed.

Hypo-electronic triple-decker sandwich complexes: synthesis and structural characterization of [(Cp*Mo)2{μ-η(6):η(6)-B4H4E-Ru(CO)3}] (E = S, Se, Te or Ru(CO)3 and Cp* = η(5)-C5Me5).

PubMed

Mondal, Bijan; Bhattacharyya, Moulika; Varghese, Babu; Ghosh, Sundargopal

2016-07-05

The syntheses and structural characterization of hypo-electronic di-molybdenum triple-decker sandwich clusters are reported. Thermolysis of [Ru3(CO)12] with an in situ generated intermediate obtained from the reaction of [Cp*MoCl4] with [LiBH4·THF] yielded an electron deficient triple-decker sandwich complex, [(Cp*Mo)2{μ-η(6):η(6)-B4H4Ru2(CO)6}], . In an effort to generate analogous triple-deckers containing group-16 elements, we isolated [(Cp*Mo)2{μ-η(6):η(6)-B4H4ERu(CO)3}] (: E = Te; : E = S; : E = Se). These clusters show a high metal coordination number and cross cluster Mo-Mo bond. The formal cluster electron count of these compounds is four or three skeletal electron pairs less than required for a canonical closo-structure of the same nuclearity. Therefore, these compounds represent a novel class of triple-decker sandwich complex with 22 or 24 valence-electrons (VE), wherein the "chair" like hexagonal middle ring is composed of B, Ru and chalcogen. One of the key differences among the synthesized triple-decker molecules is the puckering nature of the middle ring [B4RuE], which increases in the order S < Se < Ru(CO)3 < Te. In addition, Fenske-Hall and quantum-chemical calculations with DFT methods at the BP86 level of theory have been used to analyze the bonding of these novel complexes. The studies not only explain the electron unsaturation of the molecules, but also reveal the reason for the significant puckering of the middle deck. All the compounds have been characterized by IR, (1)H, (11)B, and (13)C NMR spectroscopy in solution and the solid state structures were established by crystallographic analysis.

Fatigue and changes of ATP, creatine phosphate, and lactate during the 400-m sprint.

PubMed

Hirvonen, J; Nummela, A; Rusko, H; Rehunen, S; Härkönen, M

1992-06-01

Fatigue during the 400-m sprint was studied by measuring muscle ATP, creatine phosphate (CP), lactate (M-La), and blood lactate (B-La) in six male runners before and after four experimental sprints (100, 200, 300, and 400 m). During the first 100 m, muscle CP decreased from 15.8 +/- 1.7 to 8.3 +/- 0.3 mmol/kg while M-La increased to 3.6 +/- 0.4 mmol/kg. After 200 m the CP had decreased to 6.5 +/- 0.5 mmol/kg and M-La had increased to 8.3 +/- 1.1 mmol/kg. At the end of the 400 meters, ATP and CP concentrations had decreased by 27% and 89%, respectively, and M-La had increased to 17.3 +/- 0.9 mmol/kg. It was concluded that after 200 m the speed of running decreased, although CP was not depleted and lactate concentration was not at maximum level. Complete fatigue occurred when CP stores were depleted and B-La and M-La attained an individual maximum.

Supplementation with N-3 Long-Chain Polyunsaturated Fatty Acids or Olive Oil in Men and Women with Renal Disease Induces Differential Changes in the DNA Methylation of FADS2 and ELOVL5 in Peripheral Blood Mononuclear Cells

PubMed Central

Hoile, Samuel P.; Clarke-Harris, Rebecca; Huang, Rae-Chi; Calder, Philip C.; Mori, Trevor A.; Beilin, Lawrence J.; Lillycrop, Karen A.; Burdge, Graham C.

2014-01-01

Background Studies in animal models and in cultured cells have shown that fatty acids can induce alterations in the DNA methylation of specific genes. There have been no studies of the effects of fatty acid supplementation on the epigenetic regulation of genes in adult humans. Methods and Results We investigated the effect of supplementing renal patients with 4 g daily of either n-3 long-chain polyunsaturated fatty acids (n-3 LCPUFA) or olive oil (OO) for 8 weeks on the methylation status of individual CpG loci in the 5′ regulatory region of genes involved in PUFA biosynthesis in peripheral blood mononuclear cells from men and women (aged 53 to 63 years). OO and n-3 LCPUFA each altered (>10% difference in methylation) 2/22 fatty acid desaturase (FADS)-2 CpGs, while n-3 LCPUFA, but not OO, altered (>10%) 1/12 ELOVL5 CpGs in men. OO altered (>6%) 8/22 FADS2 CpGs and (>3%) 3/12 elongase (ELOVL)-5 CpGs, while n-3 LCPUFA altered (>5%) 3/22 FADS2 CpGs and 2/12 (>3%) ELOVL5 CpGs in women. FADS1 or ELOVL2 methylation was unchanged. The n-3 PUFA supplementation findings were replicated in blood DNA from healthy adults (aged 23 to 30 years). The methylation status of the altered CpGs in FADS2 and ELOVL5 was associated negatively with the level of their transcripts. Conclusions These findings show that modest fatty acid supplementation can induce altered methylation of specific CpG loci in adult humans, contingent on the nature of the supplement and on sex. This has implications for understanding the effect of fatty acids on PUFA metabolism and cell function. PMID:25329159

Increased subsequent risk of inflammatory bowel disease association in patients with chronic pancreatitis: a nationwide population-based cohort study.

PubMed

Chen, Yu-Long; Hsu, Chin-Wang; Cheng, Cheng-Chung; Yiang, Giou-Teng; Lin, Chin-Sheng; Lin, Cheng-Li; Sung, Fung-Chang; Liang, Ji-An

2017-06-01

To investigate the relationship between chronic pancreatitis (CP) and inflammatory bowel disease (IBD) in a large population-based cohort study. Data was obtained from the Taiwan National Health Insurance Research Database. The cohort study comprised 17,796 patients newly diagnosed with CP between 2000 and 2010 and 71,164 matched controls. A Cox proportional hazards model was used for evaluating the risk of IBD in the CP and comparison cohorts. When examined with a mean follow-up period of 4.87 and 6.04 years for the CP and comparison cohorts, respectively, the overall incidence of IBD was 10.3 times higher in the CP cohort than in the comparison cohort (5.75 vs. 0.56 per 10,000 person-years). Compared with the comparison cohort, the CP cohort exhibited a higher risk of IBD, irrespective of age, sex, and presence or absence of comorbidities. Moreover, the CP cohort was associated with a significantly higher risk of Crohn's disease (adjusted hazard ratio [aHR] = 12.9, 95% confidence interval [CI] = 5.15-32.5) and ulcerative colitis (aHR = 2.80, 95% CI = 1.00-7.86). This nationwide population-based cohort study revealed a significantly higher risk of IBD in patients with CP compared with control group. Clinicians should notice this association to avoid delayed diagnosis of IBD in patients with CP.

Institutional decision to adopt Y90 as primary treatment for hepatocellular carcinoma informed by a 1,000-patient 15-year experience.

PubMed

Salem, Riad; Gabr, Ahmed; Riaz, Ahsun; Mora, Ronald; Ali, Rehan; Abecassis, Michael; Hickey, Ryan; Kulik, Laura; Ganger, Daniel; Flamm, Steven; Atassi, Rohi; Atassi, Bassel; Sato, Kent; Benson, Al B; Mulcahy, Mary F; Abouchaleh, Nadine; Asadi, Ali Al; Desai, Kush; Thornburg, Bartley; Vouche, Michael; Habib, Ali; Caicedo, Juan; Miller, Frank H; Yaghmai, Vahid; Kallini, Joseph R; Mouli, Samdeep; Lewandowski, Robert J

2017-12-01

Yttrium-90 transarterial radioembolization (TARE) is a locoregional therapy (LRT) for hepatocellular carcinoma (HCC). In this study, we present overall survival (OS) outcomes in a 1,000-patient cohort acquired over a 15-year period. Between December 1, 2003 and March 31, 2017, 1,000 patients with HCC were treated with TARE as part of a prospective cohort study. A comprehensive review of toxicity and survival outcomes was performed. Outcomes were stratified by baseline Child-Pugh (CP) class, United Network for Organ Sharing (UNOS), and Barcelona Clinic Liver Cancer (BCLC) staging systems. Albumin and bilirubin laboratory toxicities were compared to baseline. OS outcomes were reported using censoring and intention-to-treat methodologies. All treatments were outpatient, with a median one treatment per patient. Five hundred six (51%) were CP A, 450 (45%) CP B, and 44 (4%) CP C. Two hundred sixty-three (26%) patients were BCLC A, 152 (15%) B, 541 (54%) C, and 44 (4%) D. Three hundred sixty-eight (37%) were UNOS T1/T2, 169 (17%) T3, 147 (15%) T4a, 223 (22%) T4b, and 93 (9%) N/M. In CP A patients, censored OS for BCLC A was 47.3 (confidence interval [CI], 39.5-80.3) months, BCLC B 25.0 (CI, 17.3-30.5) months, and BCLC C 15.0 (CI, 13.8-17.7) months. In CP B patients, censored OS for BCLC A was 27 (CI, 21-30.2) months, BCLC B 15.0 (CI, 12.3-19.0) months, and BCLC C 8.0 (CI, 6.8-9.5) months. Forty-nine (5%) and 110 (11%) patients developed grade 3/4 albumin and bilirubin toxicities, respectively. Based on our experience with 1,000 patients over 15 years, we have made a decision to adopt TARE as the first-line transarterial LRT for patients with HCC. Our decision was informed by prospective data and incrementally reported demonstrating outcomes stratified by BCLC, applied as either neoadjuvant or definitive treatment. (Hepatology 2017). © 2017 by the American Association for the Study of Liver Diseases.

The machinability of cast titanium and Ti-6Al-4V.

PubMed

Ohkubo, C; Watanabe, I; Ford, J P; Nakajima, H; Hosoi, T; Okabe, T

2000-02-01

This study investigated the machinability (ease of metal removal) of commercially pure (CP) titanium and Ti-6Al-4V alloy. Both CP Ti and Ti-6Al-4V were cast into magnesia molds. Two types of specimens (with alpha-case and without alpha-case) were made for CP Ti and Ti-6Al-4V. Machinability (n = 5) was evaluated as volume loss (mm3) by cutting/grinding the 3.0 mm surface using fissure burs and silicon carbide (SiC) under two machining conditions: (1) two machining forces (100 or 300 gf) at two rotational speeds (15000 or 30000 rpm) for 1 min, and (2) constant machining force of 100 gf and rotational speed of 15000 rpm for 1, 2, 5, 10, and 30 min. As controls, conventionally cast Co-Cr and Type IV gold alloys were evaluated in the same manner as the titanium. When fissure burs were used, there was a significant difference in the machinability between CP titanium with alpha-case and without alpha-case. On the other hand, there was no appreciable difference in the amount of metal removed for each tested metal when using the SiC points.

In silico peptide prediction for antibody generation to recognize 5-enolpyruvylshikimate-3-phosphate synthase (EPSPS) in genetically modified organisms.

PubMed

Marani, Mariela M; Costa, Joana; Mafra, Isabel; Oliveira, Maria Beatriz P P; Camperi, Silvia A; Leite, José Roberto de Souza Almeida

2015-03-01

For the prospective immunorecognition of 5-enolpyruvylshikimate-3-phosphate synthase (CP4-EPSPS) as a biomarker protein expressed by transgenic soybean, an extensive in silico evaluation of the referred protein was performed. The main objective of this study was the selection of a set of peptides that could function as potential immunogens for the production of novel antibodies against CP4-EPSPS protein. For this purpose, the protein was in silico cleaved with trypsin/chymotrypsin and the resultant peptides were extensively analyzed for further selection of the best candidates for antibody production. The analysis enabled the successful proposal of four peptides with potential immunogenicity for their future use as screening biomarkers of genetically modified organisms. To our knowledge, this is the first attempt to select and define potential linear epitopes for the immunization of animals and, subsequently, to generate adequate antibodies for CP4-EPSPS recognition. The present work will be followed by the synthesis of the candidate peptides to be incubated in animals for antibody generation and potential applicability for the development of an immunosensor for CP4-EPSPS detection. © 2015 Wiley Periodicals, Inc.

Initial evaluation of 99m Tc-tricarbonyl-cyclopentadienyl fatty acids derivatives as SPECT tracers for myocardium.

PubMed

Liu, Jianping; Wang, Huan; Wang, Shuxia; Xue, Qianqian; Wang, Dawei; Wang, Hang; Zhang, Huabei

2017-05-15

Fatty acids are myocardial metabolic agent for detecting myocardial ischemia and infraction. However, no 99m Tc-labeled fatty acids had potential use in clinical practice. In this study, 99m Tc-CpTT-10-oxo-para-PPA (1d), 99m Tc-CpTT-11-oxo-para-PPA (2d), 99m Tc-CpTT-12-oxo-para-PPA (3d), 99m Tc-CpTT-11-oxo-ortho-PPA (4d), and 99m Tc-CpTT-11-oxo-meta-PPA (5d) were synthesized by a double ligand transfer reaction, and their biological behaviors were investigated. Compound 2d achieved good heart to blood ratio (3.39 at 5 min after intravenous), and 2d showed high-heart uptake of 6.20% ID/g at 5 minutes after injection. Compound 3d displayed a prolonged retention in the myocardium (1.43% ID/g at 60 min after injection). Radioactivity accumulation in the lungs, spleen, and blood was eliminated rapidly. In vivo, metabolite analysis presented that compound 6d may be metabolite of 2d through β-oxidation in tissue. Unfortunately, the biodistribution studies of 1d, 2d, 3d, 4d, and 5d showed fast heart clearance and poor heart to liver ratios, which suggested that the 5 99m Tc-labeled fatty acid analogues cannot be used for diagnosis. Copyright © 2017 John Wiley & Sons, Ltd.

Lithium-Rich Nanoscale Li 1.2 Mn 0.54 Ni 0.13 Co 0.13 O 2 Cathode Material Prepared by Co-Precipitation Combined Freeze Drying (CP-FD) for Lithium-Ion Batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bai, Ying; Li, Yu; Wu, Chuan

Nanoscale Li-rich Li1.2Mn0.54Ni0.13Co0.13O2 material is synthesized by a co-precipitation combined freeze drying (CP-FD) method, and compared with a conventional co-precipitation method combined vacuum drying (CP-VD). With the combination of X-ray diffraction (XRD) and scanning electron microscopy (SEM), it is found that the sample from CP-FD method consists of a pure phase with good crystallinity and small, homogenous particles (100-300 nm) with uniform particle size distribution. Inductively coupled plasma spectroscopy (ICP) shows that the sample has a stoichiometric ratio of n((Li)): n((Mn)): n((Ni)): n((Co))=9: 4: 1: 1; and its Brunauer-Emmett-Teller (BET) specific surface area is 5.749 m(2)g(-1). This sample achieves excellentmore » electrochemical properties: its initial discharge capacities are 298.9 mAhg(-1) at 0.1C (20 mAg(-1)), 246.1 mAhg(-1) at 0.5C, 215.8 mAhg(-1) at 1C, and 154.2 mAhg(-1) at 5C (5C charge and 5C discharge), as well as good cycling performance. In addition, the Li+ chemical diffusion coefficient of Li1.2Mn0.54Ni0.13Co0.13O2 material prepared by the CP-FD method is 4.59 x 10(-11) cm(2) s(-1), which is higher than that of the Li1.2Mn0.54Ni0.13Co0.13O2 material prepared by CP-VD. This phenomenon illustrates the potential for Li1.2Mn0.54Ni0.13Co0.13O2 with good rate performance synthesized by CP-FD method.« less

The series of carbon-chain complexes {Ru(dppe)Cp*}₂{μ-(C≡C )x} (x = 4–8, 11): Synthesis, structures, properties and some reactions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bruce, Michael I.; Cole, Marcus L.; Ellis, Benjamin G.

The construction of a series of compounds {Ru(dppe)Cp*} 2(μ-C 2x) (Ru*-C2x-Ru*, x = 4–8, 11)) is described. A direct reaction between RuCl(dppe)Cp* and Me 3Si(Ctriple bond; length of mdashC) 4SiMe 3 afforded Ru*-C8-Ru* in 89% yield. The Pd(0)/Cu(I)-catalysed coupling of Ru{Ctriple bond; length of mdashCCtriple bond; length of mdashCAu(PPh 3)}(dppe)Cp*Ru*-C4-Au (2 equiv.) with diiodoethyne gave Ru*-C10-Ru* (64%), or of 1 equiv. with I(Ctriple bond; length of mdashC) 3I gave Ru*-C14-Ru* (36%); similarly, Ru{(Ctriple bond; length of mdashC) 4Au(PPh 3)}(dppe)Cp*Ru*-C8-Au and I(Ctriple bond; length of mdashC) 3I gave Ru*-C22-Ru* (12%). Desilylation (TBAF) of Ru{(Ctriple bond; length of mdashC)xSiMe 3}(dppe)Cp*Ru*-C2x-Si (x =more » 3, 4) followed by oxidative coupling [Cu(OAc) 2/py] gave Ru*-C12-Ru* (82%) and Ru*-C16-Ru* (58%), respectively. Similar oxidative coupling of Ru(Ctriple bond; length of mdashCCtriple bond; length of mdashCH)(dppe)Cp* was a second route to Ru*-C8-Ru* (82%). Appropriate precursors are already known, or obtained by coupling of Ru*-C2x-Si (x = 2, 4) with AuCl(PPh 3)/NaOMe [Ru*-C4-Au, 95%; Ru*-C8-Au, 74%] or from Pd(0)/Cu(I) catalysed coupling of Ru*-C2x-Au (x = 2, 3) with I(Ctriple bond; length of mdashC) 2SiMe 3 (Ru*-C8-Si, 64%; Ru*-C10-Si, 2%). Reactions between Ru*-C2x-Ru* (x = 3, 4) and Fe 2(CO) 9 gave {Fe 3(CO) 9}{μ 3-CCtriple bond; length of mdashC[Ru(dppe)Cp*]} 2Fe(C 3-Ru*) 2 and {Fe 3(CO) 9}{μ 3-CCtriple bond; length of mdashC[Ru(dppe)Cp*]}{μ 3-C(Ctriple bond; length of mdashC) 2[Ru(dppe)Cp*]} Fe(C 3-Ru*)(C 5-Ru*), respectively. The redox properties of the series of complexes with 2x = 2–16 were measured and showed a diminution of the separation of the first two oxidation potentials, ΔE = E 2 - E 1, with increasing carbon chain length. The X-ray-determined molecular structures of Ru*-C8-Si, Ru*-C8-Ru*, Ru*-C14-Ru* (two C 6H 6 solvates), {Ru(PPh 3) 2Cp} 2{μ-(Ctriple bond; length of mdashC) 4}·4CHCl 3Ru-C 8-Ru·4CHCl 3 and of Fe(C 3-Ru*) 2 and Fe(C 3-Ru*)(C 5-Ru*) are reported.« less

Surgical treatment for Ellis type 3 coronary perforation during percutaneous catheter intervention.

PubMed

Totsugawa, Toshinori; Kuinose, Masahiko; Yoshitaka, Hidenori; Katayama, Keijiro; Tsushima, Yoshimasa; Ishida, Atsuhisa; Chikazawa, Genta; Hiraoka, Arudo

2012-01-01

Coronary perforation (CP) is a rare, but sometimes lethal, complication of percutaneous catheter intervention (PCI). We reviewed surgically-treated cases of type 3 CP during PCI. From 2007 to 2010, 5 patients underwent surgical repair for type 3 CP (3 men, 2 women; mean age, 74 years). The mean number of diseased coronary branches was 2.6 and the mean SYNTAX score was 45. The target lesions were the left anterior descending artery in 4 cases and the right coronary artery in 1 case. Types of American Heart Association/American College of Cardiology classification were type B2 in only one case and type C in 4 cases. The causes of perforation were balloon inflation in 4 patients and rotational atherectomy in 1 patient. The in-hospital mortality rate was 20%. In the cases of CP associated with balloon inflation, coronary lacerations were so severe that re-bleeding occurred even if the covered stent could temporarily achieve hemostasis, and percutaneous cardiopulmonary support and emergency surgery were required. CP induced by balloon inflation tends to result in a serious condition compared with rotablator-induced CP. Surgery should be immediately performed even after covered stent implantation if there is any possibility of re-bleeding in the case of balloon-induced type 3 CP.

Ischemic preconditioning enhances critical power during a 3 minute all-out cycling test.

PubMed

Griffin, Patrick J; Ferguson, Richard A; Gissane, Conor; Bailey, Stephen J; Patterson, Stephen D

2018-05-01

This study tested the hypothesis that ischemic preconditioning (IPC) would increase critical power (CP) during a 3 minute all-out cycling test. Twelve males completed two 3 minute all-out cycling tests, in a crossover design, separated by 7 days. These tests were preceded by IPC (4 x 5 minute intervals at 220 mmHg bilateral leg occlusion) or SHAM treatment (4 x 5 minute intervals at 20 mmHg bilateral leg occlusion). CP was calculated as the mean power output during the final 30 s of the 3 minute test with W' taken as the total work done above CP. Muscle oxygenation was measured throughout the exercise period. There was a 15.3 ± 0.3% decrease in muscle oxygenation (TSI; [Tissue saturation index]) during the IPC stimulus, relative to SHAM. CP was significantly increased (241 ± 65 W vs. 234 ± 67 W), whereas W' (18.4 ± 3.8 vs 17.9 ± 3.7 kJ) and total work done (TWD) were not different (61.1 ± 12.7 vs 60.8 ± 12.7 kJ), between the IPC and SHAM trials. IPC enhanced CP during a 3 minute all-out cycling test without impacting W' or TWD. The improved CP after IPC might contribute towards the effect of IPC on endurance performance.

Utility of Lithium in Rare-Earth Metal Reduction Reactions to Form Nontraditional Ln2+ Complexes and Unusual [Li(2.2.2-cryptand)]1+ Cations.

PubMed

Huh, Daniel N; Darago, Lucy E; Ziller, Joseph W; Evans, William J

2018-02-19

The utility of lithium compared to other alkali metals in generating Ln 2+ rare-earth metal complexes via reduction of Ln 3+ precursors in reactions abbreviated as LnA 3 /M (Ln = rare-earth metal; A = anionic ligand; M = alkali metal) is described. Lithium reduction of Cp' 3 Ln (Cp' = C 5 H 4 SiMe 3 ; Ln = Y, Tb, Dy, Ho) under Ar in the presence of 2.2.2-cryptand (crypt) forms new examples of crystallographically characterizable Ln 2+ complexes of these metals, [Li(crypt)][Cp' 3 Ln]. In each complex, lithium is found in an N 2 O 4 donor atom coordination geometry that is unusual for the cryptand ligand. Magnetic susceptibility data on these new examples of nontraditional divalent lanthanide complexes are consistent with 4f n 5d 1 electronic configurations. The Dy and Ho complexes have exceptionally high single-ion magnetic moments, 11.35 and 11.67 μ B , respectively. Lithium reduction of Cp' 3 Y under N 2 at -35 °C forms the Y 2+ complex (Cp' 3 Y) 1- , which reduces dinitrogen upon warming to room temperature to generate the (N 2 ) 2- complex [Cp' 2 Y(THF)] 2 (μ-η 2 :η 2 -N 2 ). These results provide insight on the factors that lead to reduced dinitrogen complexes and/or stable divalent lanthanide complexes as a function of the specific reducing agent and conditions.

Targeting the middle region of CP4-EPSPS protein for its traceability in highly processed soy-related products.

PubMed

Wu, Honghong; Wang, Xiaofu; Zhou, Xinghu; Zhang, Yihua; Huang, Ming; He, Jian; Shen, Wenbiao

2017-09-01

Transgenic components in genetically modified organisms consist not only of the transgenic genes, but also the transgenic protein. However, compared with transgenic DNA, less attention has been paid to the detection of expressed protein, especially those degraded from genetically modified soybean after food processing. In this study, the full length 5-enolpyruvyl-shikimate-3-phosphate synthase (CP4-EPSPS, 47.6 kD) protein was probed with the SC-16 (S19-R33) and the DC-16 (D219-K233) polyclonal antibodies in immunoblots. Both antibodies were able to detect the full length CP4-EPSPS and its residues in soy powder made from Roundup-Ready soybeans after heating and microwaving treatments which also reduced the molecular weight of the protein to 45.8 and 38.7 kD, respectively. Taken together the immunoblot results suggest that the middle region of the CP4-EPSPS protein possessed better stability than its N-terminal during thermal processing. This deduction was further validated by autoclave treatment, where a 37.4 kD residue of the protein was recognized by DC-16. A similar result was obtained in processed smoked sausage containing Roundup Ready soybean protein isolate (as an extender). The additional use of a further polyclonal antibody CK-17 (C372-K388), showed that compared with only the one signal for CP4-EPSPS detected by the SC-16 and CK-17 antibodies, the DC-16 middle region antibody detected four signals for CP4-EPSPS from five market sourced soy protein concentrates. Taken together, the study suggested that the middle region of CP4-EPSPS was more useful than the N- and C-terminal for tracing transgenic CP4-EPSPS protein and its remnants in highly processed soy-related products.

The effects of salinity on nitrification using halophilic nitrifiers in a Sequencing Batch Reactor treating hypersaline wastewater.

PubMed

Cui, You-Wei; Zhang, Hong-Yu; Ding, Jie-Ran; Peng, Yong-Zhen

2016-04-25

With annual increases in the generation and use of saline wastewater, the need to avoid environmental problems such as eutrophication is critical. A previous study identified ways to start up a halophilic sludge domesticated from estuarine sediments to remove nitrogen from wastewater with a salinity of 30 g/L. This investigation expands that work to explore the impact of salinity on nitrogen removal. This study demonstrated that the mixed halophilic consortia removed nitrogen from wastewater with a salinity of 30-85 g/L. A kinetic analysis showed that halophilic nitrifiers selected based on hypersalinity were characterized by low Ks, μmax and specific ammonium oxidization rates. This explains the decrease in ammonium removal efficiency in the high salinity operational phases. Salinity inhibited ammonia oxidizing bacteria (AOB) activity, as well as the number of dominant AOB, but did not significantly affect the AOB dominant species. Three most dominant AOB lineages in the halophilic sludge were Nitrosomonas marina, Nitrosomonas europaea, and Nitrosococcus mobilis. Nitrosomonas europaea and Nitrosococcus mobilis were mainly affected by salinity, while nitrite accumulation and ammonia loading played the key role in determining the abundance of Nitrosococcus mobilis and Nitrosococcus europaea. The study contributes insights about shifts in halophilic nitrifying bacterial populations.

The effects of salinity on nitrification using halophilic nitrifiers in a Sequencing Batch Reactor treating hypersaline wastewater

PubMed Central

Cui, You-Wei; Zhang, Hong-Yu; Ding, Jie-Ran; Peng, Yong-Zhen

2016-01-01

With annual increases in the generation and use of saline wastewater, the need to avoid environmental problems such as eutrophication is critical. A previous study identified ways to start up a halophilic sludge domesticated from estuarine sediments to remove nitrogen from wastewater with a salinity of 30 g/L. This investigation expands that work to explore the impact of salinity on nitrogen removal. This study demonstrated that the mixed halophilic consortia removed nitrogen from wastewater with a salinity of 30–85 g/L. A kinetic analysis showed that halophilic nitrifiers selected based on hypersalinity were characterized by low Ks, μmax and specific ammonium oxidization rates. This explains the decrease in ammonium removal efficiency in the high salinity operational phases. Salinity inhibited ammonia oxidizing bacteria (AOB) activity, as well as the number of dominant AOB, but did not significantly affect the AOB dominant species. Three most dominant AOB lineages in the halophilic sludge were Nitrosomonas marina, Nitrosomonas europaea, and Nitrosococcus mobilis. Nitrosomonas europaea and Nitrosococcus mobilis were mainly affected by salinity, while nitrite accumulation and ammonia loading played the key role in determining the abundance of Nitrosococcus mobilis and Nitrosococcus europaea. The study contributes insights about shifts in halophilic nitrifying bacterial populations. PMID:27109617

A descriptive comparison of sprint cycling performance and neuromuscular characteristics in able-bodied athletes and paralympic athletes with cerebral palsy.

PubMed

Runciman, Phoebe; Derman, Wayne; Ferreira, Suzanne; Albertus-Kajee, Yumna; Tucker, Ross

2015-01-01

This study investigated the sprint cycling performance and neuromuscular characteristics of Paralympic athletes with cerebral palsy (CP) during a fatiguing maximal cycling trial compared with those of able-bodied (AB) athletes. Five elite athletes with CP and 16 AB age- and performance-matched controls performed a 30-sec Wingate cycle test. Power output (W/kg) and fatigue index (%) were calculated. Electromyography was measured in five bilateral muscles and expressed in mean amplitude (mV) and median frequency (Hz). Power output was significantly higher in the AB group (10.4 [0.5] W/kg) than in the CP group (9.8 [0.5] W/kg) (P < 0.05). Fatigue index was statistically similar between the AB (27% [0.1%]) and CP (25% [0.1%]) groups. Electromyographic mean amplitude and frequency changed similarly in all muscle groups tested, in both affected and nonaffected sides, in the CP and AB groups (P < 0.05). Neuromuscular irregularities were identified in the CP group. The similarity in fatigue between the CP and AB groups indicates that elite athletes with CP may have a different exercise response to others with CP. The authors propose that this may result from high-level training over many years. This has rehabilitative implications, as it indicates near-maximal adaptation of the CP body toward normal levels.

Effect of a 5-min cold-water immersion recovery on exercise performance in the heat.

PubMed

Peiffer, J J; Abbiss, C R; Watson, G; Nosaka, K; Laursen, P B

2010-05-01

This study examined the effect of a 5-min cold-water immersion (14 degrees C) recovery intervention on repeated cycling performance in the heat. 10 male cyclists performed two bouts of a 25-min constant-paced (254 (22) W) cycling session followed by a 4-km time trial in hot conditions (35 degrees C, 40% relative humidity). The two bouts were separated by either 15 min of seated recovery in the heat (control) or the same condition with 5-min cold-water immersion (5th-10th minute), using a counterbalanced cross-over design (CP(1)TT(1) --> CWI or CON --> CP(2)TT(2)). Rectal temperature was measured immediately before and after both the constant-paced sessions and 4-km timed trials. Cycling economy and Vo(2) were measured during the constant-paced sessions, and the average power output and completion times were recorded for each time trial. Compared with control, rectal temperature was significantly lower (0.5 (0.4) degrees C) in cold-water immersion before CP(2) until the end of the second 4-km timed trial. However, the increase in rectal temperature (0.5 (0.2) degrees C) during CP(2) was not significantly different between conditions. During the second 4-km timed trial, power output was significantly greater in cold-water immersion (327.9 (55.7) W) compared with control (288.0 (58.8) W), leading to a faster completion time in cold-water immersion (6.1 (0.3) min) compared with control (6.4 (0.5) min). Economy and Vo(2) were not influenced by the cold-water immersion recovery intervention. 5-min cold-water immersion recovery significantly lowered rectal temperature and maintained endurance performance during subsequent high-intensity exercise. These data indicate that repeated exercise performance in heat may be improved when a short period of cold-water immersion is applied during the recovery period.

Effect of dietary crude protein levels in a commercial range, on the nitrogen balance, ammonia emission and pollutant characteristics of slurry in fattening pigs.

PubMed

Hernández, F; Martínez, S; López, C; Megías, M D; López, M; Madrid, J

2011-06-01

An experiment was conducted to investigate the effect of dietary levels of crude protein (CP), close to the range used commercially and to the European Commission recommended values, on the nitrogen (N) balance, ammonia (NH(3)) emission and pollutant characteristics of the slurry from growing and finishing pigs. Three feeding programmes with different CP levels were compared during the growing and the finishing periods of fattening. Diets were formulated to be isoenergetic and for the digestible lysine : metabolisable energy ratio to be similar in all the diets for each phase, but differed in CP concentration (160, 150 and 140 g CP/kg for the growing phase and 155, 145 and 135 g CP/kg for the finishing phase). Faeces and urine from barrows (eight replicates per diet) allocated in metabolism cages were collected separately for 5 days to calculate the N balance and for 2 days to measure NH(3) emission in a laboratory system for 240 h. Excreta were analysed for pH, volatile fatty acids (VFA), total N, electrical conductivity (EC), total solids (TS), volatile solids (VS), biochemical oxygen demand (BOD(5)), chemical oxygen demand (COD) and NH(4)-N reduction of dietary CP content led to a linear decrease of urinary (P < 0.05) and total (P < 0.05) N excretion, and N excretion/feed intake (P < 0.001). The emission of NH3 was similar in all diets (P > 0.05) during the 240 h of study. However, in the growing phase, the NH(3)-N level in slurry was lower (P < 0.05) for the low-CP diet. In addition, the CP level had no significant effect (P > 0.05) on total VFA, EC, TS, VS, COD or BOD(5) contents of excreta. These parameters were higher (P < 0.05) in slurry from the finishing phase than from the growing phase. However, NH(4)-N in the slurry decreased (P < 0.05) by 20.3% and 28.4% when the CP level was decreased by 9.30 or 21.40 g/kg, respectively. It is concluded that lowering dietary CP levels even by small amounts and using CP levels close to these used in commercial diets and close to the European Commission recommended values will decrease urinary and total N excretion in the slurry of growing-finishing pigs. The slurry from finishing pigs is more concentrated than that from growing pigs.

Protective effect of combined pumpkin seed and ginger extracts on sperm characteristics, biochemical parameters and epididymal histology in adult male rats treated with cyclophosphamide.

PubMed

Aghaie, Somaieh; Nikzad, Hossein; Mahabadi, Javad Amini; Taghizadeh, Mohsen; Azami-Tameh, Abolfazl; Taherian, Aliakbar; Sajjadian, Seyyed Mohammad Sajjad; Kamani, Mehran

2016-09-01

Reproductive toxicity is one of the side effects of cyclophosphamide (CP) in cancer treatment. Pumpkin seeds and Zingiber officinale are natural sources of antioxidants. We investigated the possible protective effect of combined pumpkin seed and Zingiber officinale extracts on sperm characteristics, epididymal histology and biochemical parameters of CP-treated rats. Male adult Wistar rats were divided randomly into six groups. Group 1, as a control, received an isotonic saline solution injection intraperitoneally (IP). Group 2 were injected IP with a single dose of CP (100 mg/kg) once. Groups 3 and 4 received CP plus 300 and 600 mg/kg combined pumpkin seed and Zingiber officinale extract (50:50). Groups 5 and 6 received only 300 and 600 mg/kg combined pumpkin seed and Zingiber officinale extract. Six weeks after treatment, sperm characteristics, histopathological changes and biochemical parameters were assessed. In CP-treated rats, motile spermatozoa were decreased, and abnormal or dead spermatozoa increased significantly (P < 0.001) but administration of the mixed extract improved sperm parameters. Epididymal epithelium and fibromascular thickness were also improved in extract-treated rats compared to control or CP groups. Biochemical analysis showed that the administration of combined extracts could increase the total antioxidant capacity (TAC) level significantly in groups 3, 4, 5 and 6. Interestingly, the mixed extract could decrease most of the side effects of CP such as vacuolization and separation of epididymal tissue. Our findings indicated that the combined extracts might be used as a protective agent against CP-induced reproductive toxicity.

Controlling of growth performance, lipid deposits and fatty acid composition of chicken meat through a probiotic, Lactobacillus johnsonii during subclinical Clostridium perfringens infection.

PubMed

Wang, Hesong; Ni, Xueqin; Liu, Lei; Zeng, Dong; Lai, Jing; Qing, Xiaodan; Li, Guangyao; Pan, Kangcheng; Jing, Bo

2017-02-10

Meat is considered as a major source of polyunsaturated fatty acid (PUFA) which is essential for humans, therefore its lipid level and fatty acid composition have drawn great attention. As no clinical sign can be found in chicks subclinically infected by Clostridium perfringens (CP), the meat may be purchased and eaten. The objective of the present study was to determine whether Lactobacillus johnsonii (LJ) can control the CP-caused impact on growth, lipid levels, fatty acid composition and other flavor or nutritional quality in the meat. 480 one-day-old chicks were divided into four groups and fed with basal diet (control and CP group). Supplemented with 1 × 10 5 (L-LJ) and 1 × 10 6 (H-LJ) colony-forming unit (cfu), CP diet was fed for 42 days. From day 19 to 22, birds of CP and LJ groups were administered with CP twice per day and the control was administered with liver broth. LJ-treated chickens were free from negative influences on growth performance and significant decrease of abdominal fat deposit., LJ inhibited CP-caused shearing force and drip loss increase and pH 40 min and 24 h decrease after sacrifice. In addition, LJ exhibited a positive effect on muscle lipid peroxidation by significantly increasing SOD, CAT and GSH-Px activity and decreasing MDA level. Besides, LJ attenuated the decrease of intramuscular fat, total cholesterol and triglyceride contents caused by CP infection. However, levels of total protein and most of amino acids were not changed. CP infection decreased C18:3n-3 (α-LA), C20:4n-6, C20:5n-3(EPA), C22:4n-6, C22:5n-3, C22:6n-3(DHA), total PUFA, n-3 PUFA and PUFA:SFA ratio and increased C14:0, total SFA and n-6:n-3 ratio. LJ was found to protect the muscle from these changes. Meanwhile, the 28-day gut permeability level was higher in CP group. These findings suggest that CP may affect the growth performance of chicks and negatively influence lipid content and fatty acid composition in chicken meat. Meanwhile, LJ treatment may be effective in controlling these changes by reducing the increased gut permeability caused by CP subclinical infection.

Silylene extrusion from organosilanes via double geminal Si-H bond activation by a Cp*Ru(kappa2-P,N)+ complex: observation of a key stoichiometric step in the glaser-tilley alkene hydrosilylation mechanism.

PubMed

Rankin, Matthew A; MacLean, Darren F; Schatte, Gabriele; McDonald, Robert; Stradiotto, Mark

2007-12-26

Treatment of Cp*RuCl(kappa2-P,N-2b) (2b = 2-NMe2-3-PiPr2-indene) with TlSO3CF3 produced the cyclometalated complex [4]+SO3CF3- in 94% isolated yield. Exposure of [4]+X- (X = B(C6F5)4 or SO3CF3) to Ph2SiH2 (10 equiv) or PhSiH3 afforded the corresponding [Cp*(mu-P,N-2b)(H)2Ru=SiRPh]+X- complexes, [5]+X- (R = Ph; X = B(C6F5)4, 82%; X = SO3CF3, 39%) and [6]+X- (R = H; X = B(C6F5)4, 94%; X = SO3CF3, 95%). Notably, these transformations represent the first documented examples of Ru-mediated silylene extrusion via double geminal Si-H bond activation of an organosilane-a key step in the recently proposed Glaser-Tilley (G-T) alkene hydrosilylation mechanism. Treatment of [5]+B(C6F5)4- with KN(SiMe3)2 or [6]+SO3CF3- with NaN(SiMe3)2 afforded the corresponding zwitterionic Cp*(mu-2-NMe2-3-PiPr2-indenide)(H)2Ru=SiRPh complex in 69% (R = Ph, 7) or 86% (R = H, 8) isolated yield. Both [6]+X- and 8 proved unreactive toward 1-hexene and styrene and provided negligible catalytic turnover in the attempted metal-mediated hydrosilylation of these substrates with PhSiH3, thereby providing further empirical evidence for the required intermediacy of base-free Ru=Si species in the G-T mechanism. Isomerization of the P,N-indene ligand backbone in [6]+X-, giving rise to [Cp*(mu-1-PiPr2-2-NMe2-indene)(H)2Ru=SiHPh]+X- ([9]+X-), was observed. In the case of [9]+SO3CF3-, net intramolecular addition of the Ru=Si-H group across the styrene-like C=C unit within the ligand backbone to give 10 (96% isolated yield) was observed. Crystallographic characterization data are provided for [4]+X-, [5]+X-, [6]+X-, 8, and 10.

Molecular typing and antimicrobial susceptibility of Clostridium perfringens from broiler chickens.

PubMed

Gharaibeh, Saad; Al Rifai, Rami; Al-Majali, Ahmad

2010-12-01

Clostridium perfringens (Cp) causes necrotic enteritis disease in commercial poultry. Antimicrobials are used to control and treat this disease and sometimes clinical outbreaks do not respond well to certain treatments. This study was designed to isolate Cp from clinical cases, type these isolates by multiplex PCR, and determine their antimicrobial susceptibility by micro-dilution method. A total of 67 Cp isolates were obtained from 155 broiler chicken flocks. All isolates were classified as type A and non-enterotoxin producers. Lincomycin, erythromycins, and tilmicosin showed very high minimal inhibitory concentration (MIC) 50 of ≥256 μg/ml. However, tylosin, amoxicillin, ampicillin, penicillin, florfenicol, danofloxacin, enrofloxacin, chlortetracycline, doxycycline, and oxytetracycline had variable MIC₅₀ of 64, 0.5, 1, 1, 8, 4, 8, 4, 8, 0.5 μg/ml, respectively. It is recommended that Cp infections in Jordan be treated with either penicillins or tetracyclines especially amoxicillin and oxytetracycline. Copyright © 2010 Elsevier Ltd. All rights reserved.

Synthesis and Biological Activity of Phospholipase C-Resistant Analogues of Phosphatidylinositol 4, 5-bisphosphate

PubMed Central

Zhang, Honglu; Xu, Yong; Zhang, Zheng; Liman, Emily R.; Prestwich, Glenn D

2008-01-01

The membrane phospholipid phosphatidylinositol 4,5-bisphosphate (PtdIns(4,5)P2) is an important regulator in cell physiology. Hydrolysis of PtdIns(4,5)P2 by phospholipase C (PLC) releases two second messengers, Ins(1,4,5)P3 and diacylglycerol. To dissect the effects of PtdIns(4,5)P2 from those resulting from PLC-generated signals, a metabolically-stabilized analogue of PtdIns(4,5)P2 was required. Two analogues were designed in which the scissile O-P bond was replaced with a C-P bond that could not be hydrolyzed by PLC activity. Herein we describe the asymmetric total synthesis of the first metabolically-stabilized, phospholipase C-resistant analogues of PtdIns(4,5)P2. The key transformation was a Pd(0)-catalyzed coupling of an H-phosphite with a vinyl bromide to form the desired C-P linkage. The phosphonate analogues of PtdIns(4,5)P2 were found to be effective in restoring the sensitivity of the TRPM4 channel to Ca2+ activation. PMID:16637624

Ligand Effects in Aluminum Cluster based Energetic Materials

DTIC Science & Technology

2017-09-01

was recently reported and the effect of their increased steric bulk is discussed here. Experimental results and density functional theory (DFT...analysis show that these clusters are enthalpically more stable than the Cp* variant, due primarily to non -covalent interactions (NCIs) across ligand...C5Me4iPr), two clusters similar to Al4Cp*4, was recently reported and the effect of their increased steric bulk is discussed here. Experimental

Chronic prostatitis/chronic pelvic pain syndrome in adolescents compared with that in young adults.

PubMed

Lee, Keon-Cheol; Cho, In-Rae

2017-07-01

Chronic prostatitis (CP)/chronic pelvic pain syndrome (CPPS) has been studied mainly in adults; reports in adolescents are rare. We compared the clinical characteristics of adolescent CP/CPPS patients with those of young adults. We retrospectively analyzed 20 adolescents with CP/CPPS aged <20 years who visited our outpatient department from August 2005 to April 2012. The control group comprised 120 young adult CP/CPPS patients. A complete medical history, physical examination, the national institute of health-chronic prostatitis symptoms index (NIH-CPSI) questionnaire, urinalysis, expressed prostatic secretion (EPS) or semen analysis, transrectal prostate ultrasonography, and prostate-specific antigen (PSA) were performed. Based on the EPS or semen analysis, patients were divided into category III-A or III-B. The mean age was 16.5±2.0 and 32.8±5.0 years in the adolescent and control groups, respectively. A sexual activity history was seen in 2 patients; 9 and 11 patients were in category III-A and III-B, respectively. The PSA was 0.65±0.39 and 1.22±0.48 ng/mL in the adolescent and control groups, respectively. The prostate size was 12.4±4.4 and 21.0±4.9 g in the adolescent and control groups, respectively. The NIH-CPSI scores in the adolescent group were 9.2±5.2, 5.5±3.5, 7.5±3.2, and 22.2±8.1 for pain, voiding, quality of life (QoL) domains, and total scores, respectively. The adolescent group showed a tendency to exhibit high voiding symptom scores. CPPS has an equally severe impact on QoL in adults and adolescents. Apart from high voiding symptom scores in adolescents, no difference was found in terms of urologic clinical parameters.

The preparation, characterisation and in vitro cytotoxicity of potentially chemotherapeutic heterobimetallic complexes containing early and late transition metals.

PubMed

Wedgwood, Janet L; Kresinski, Roman A; Merry, Stephen; Platt, Andrew W G

2003-06-01

The reactions of phosphine Ph(2)P(CH(2))(2)SO(3)Na with Cp(2)M'Cl(2) (M'=Ti, Zr) in aqueous solution give the metallophosphines, Cp(2)Ti(OSO(2)(CH(2))(2)PPh(2))(2) (Cp=cyclopentadienyl) and CpZr(OH)(OSO(2)(CH(2))(2)PPh(2))(2). These react with CODM"Cl(2) (M"=Pd, Pt) (COD=1,5-cyclooctadiene) in dichloromethane to give heterobimetallic complexes Cp(2)Ti(OSO(2)(CH(2))(2)PPh(2))(2)M"Cl(2) and CpZr(OH)(OSO(2)(CH(2))(2) PPh(2))(2)M"Cl(2) respectively. The compounds are characterised by infrared and NMR spectroscopies and elemental analysis. Electrospray mass spectra of the complexes are reported and compared to those of Cp(2)M'Cl(2) in water and dimethylsulfoxide (DMSO). For zirconocene dichloride and its product heterobimetallic complexes, the addition of ethylenediamine tetraacetic acid disodium salt (Na(2)H(2)EDTA) was found to be an effective ionisation enhancement agent for the electrospray mass spectral studies. Cytotoxicity studies for the previously reported Cl(2)Pt(PPh(2)(CH(2))(2)SO(3)H)(2).3.5H(2)O (Wedgwood et al., Inorg. Chim. Acta 290 (1999) 189), and the compounds Cp(2)Ti(OSO(2)(CH(2))(2) PPh(2))(2).1.5H(2)O and Cp(2)Ti(OSO(2)(CH(2))(2)PPh(2))(2)PtCl(2).4H(2)O reported here, have been evaluated by colony formation assay against cisplatin-sensitive and -resistant cell lines L929 and L929/R to highlight potential chemotherapeutic activity. The compound Cl(2)Pt(PPh(2)(CH(2))(2)SO(3)H)(2).3.5H(2)O overcomes cisplatin resistance.

Diketo modification of curcumin affects its interaction with human serum albumin.

PubMed

Shaikh, Shaukat Ali M; Singh, Beena G; Barik, Atanu; Ramani, Modukuri V; Balaji, Neduri V; Subbaraju, Gottumukkala V; Naik, Devidas B; Indira Priyadarsini, K

2018-06-15

Curcumin isoxazole (CI) and Curcumin pyrazole (CP), the diketo modified derivatives of Curcumin (CU) are metabolically more stable and are being explored for pharmacological properties. One of the requirements in such activities is their interaction with circulatory proteins like human serum albumin (HSA). To understand this, the interactions of CI and CP with HSA have been investigated employing absorption and fluorescence spectroscopy and the results are compared with that of CU. The respective binding constants of CP, CI and CU with HSA were estimated to be 9.3×10 5 , 8.4×10 5 and 2.5×10 5 M -1 , which decreased with increasing salt concentration in the medium. The extent of decrease in the binding constant was the highest in CP followed by CI and CU. This revealed that along with hydrophobic interaction other binding modes like electrostatic interactions operate between CP/CI/CU with HSA. Fluorescence quenching studies of HSA with these compounds suggested that both static and dynamic quenching mechanisms operate, where the contribution of static quenching is higher for CP and CI than that for CU. From fluorescence resonance energy transfer studies, the binding site of CU, CI and CP was found to be in domain IIA of HSA. CU was found to bind in closer proximity with Trp214 as compared to CI and CP and the same was responsible for efficient energy transfer and the same was also established by fluorescence anisotropy measurements. Furthermore docking simulation complemented the experimental observation, where both electrostatic as well as hydrophobic interactions were indicated between HSA and CP, CI and CU. This study is useful in designing more stable CU derivatives having suitable binding properties with proteins like HSA. Copyright © 2018 Elsevier B.V. All rights reserved.

Study of the phase transition in lithium potassium rubidium sulfate system

NASA Astrophysics Data System (ADS)

Hamed, A. E.; Abd. El-Aziz, Y. M.; Madi, N. K.; Kassem, M. E.

1998-10-01

Specific heat, Cp, measurements have been performed in lithium potassium rubidium sulfate, (Li 0.5- x/2 K 0.5- x/2 Rb x) 2SO 4, system in a wide range of Rb 2SO 4 content ( x) ( x=0 up to x=10%). Measurements were made between 300 and 800 K with special attention paid to the phase transition at 708 K. It is shown that for small contents, ( x), ( x=0.2 up to x=2%) quantitative changes in the temperature dependence of specific heat Cp( T) around the transition point, T1, are observed. A larger content, x, results in essential changes in the critical behavior of Cp( T) and a considerable change in the phase transition accompanied by a progressive decrease in the thermodynamic parameters. The ratios of the Landau expansion coefficients change as the content of Rb 2SO 4 increases.

Excretion, metabolism, and pharmacokinetics of CP-945,598, a selective cannabinoid receptor antagonist, in rats, mice, and dogs.

PubMed

Miao, Zhuang; Scott, Dennis O; Griffith, David A; Day, Robert; Prakash, Chandra

2011-12-01

1-(8-(2-Chlorophenyl)-9-(4-chlorophenyl)-9H-purin-6-yl)-4-(ethylamino)piperidine-4-carboxamide (CP-945,598) is an orally active antagonist of the cannabinoid CB-1 receptor that progressed into phase 3 human clinical trials for the treatment of obesity. In this study, we investigated the metabolic fate and disposition of CP-945,598 in rats, Tg-RasH2 mice, and dogs after oral administration of a single dose of [(14)C]CP-945,598. Total mean recoveries of the radioactive dose were 97.7, 97.8, and 99.3% from mice, rats, and dogs, respectively. The major route of excretion in all three species was via the feces, but on the basis of separate studies in bile duct-cannulated rats and dogs, this probably reflects excretion in bile rather than incomplete absorption. CP-945,598 underwent extensive metabolism in all three species, because no unchanged parent compound was detected in the urine across species. The primary metabolic pathway of CP-945,598 involved N-deethylation to form an N-desethyl metabolite (M1). M1 was subsequently metabolized by amide hydrolysis, oxidation, and ribose conjugation to numerous novel and unusual metabolites. The major circulating and excretory metabolites were species-dependent; however, several common metabolites were observed in more than one species. In addition to parent compound, M1, M3, M4, and M5 in rats, M1, M3, and M4 in mice, and M1 and M2 in dogs were identified as the major circulating metabolites. Gender-related differences were also apparent in the quantitative and qualitative nature of the metabolites in rats. An unprecedented metabolite, M4, formed by deamidation of M1 or M3 (N-hydroxy-M1), but not by decarboxylation of M2, was identified in all species. M4 was nonenzymatically converted to M5.

Decreased plasma levels of ceruloplasmin after diet-induced weight loss in obese women.

PubMed

Tajik, N; Golpaie, A; Keshavarz, S A; Djalali, M; Sehat, M; Masoudkabir, F; Ahmadivand, Z; Fatehi, F; Zare, M; Yazdani, T

2012-06-01

Plasma ceruloplasmin (Cp) has been shown to be a risk factor for cardiovascular disease and also to be associated with obesity. However, it is not known whether weight loss could decrease the plasma Cp levels. To investigate the effect of diet-induced weight loss on plasma Cp in obese women. Sixty-seven healthy obese women [age =33.4±8.7 yr, body mass index (BMI) =36.0±4.8 kg/m2] were entered into a medically supervised program aimed at reducing body weight by 10% or more. Weight loss was achieved through a diet providing a daily energy deficit of 500-1000 kcal/day. In addition, all patients were prescribed to use 50 g of a fiber supplement per day. For all subjects, assessment of dietary intake, anthropometric indices, and plasma levels of C-reactive protein and Cp was performed at the first visit and repeated at 12th week of follow-up. By completing the program, weight (Δ=-9.5%, p<0.0001), BMI (Δ=-9.7%, p<0.0001), waist-circumference (Δ=-6.1%, p<0.0001), and triceps skinfold thickness (Δ=-14.9%, p<0.0001) significantly decreased. Plasma Cp significantly decreased after 12 weeks of dietary intervention (33.6±5.6 mg/dl vs 25.2±5.8 mg/dl, p<0.0001). Percent change in Cp was correlated with percent change in waist-circumference (r=446, p=0.015). Our study suggests that an improved body composition induced by restriction of energy intake is associated with decreased serum concentrations of Cp in obese women which in turn might have reduced the subjects' risk of developing cardiovascular disease.

The 3-min all-out test is valid for determining critical power but not anaerobic work capacity in tethered running

PubMed Central

2018-01-01

The purpose of the study was to investigate if the 3-min all-out test (3MT) is valid for obtaining critical power intensity (CP) and the amount of work that can be performed above CP (W’) on non-motorized treadmills in tethered running. Eight physically active individuals (24 ± 3 years; 78.3 ± 8.7 kg; 179 ± 5 cm; 9.0 ± 2.5% body fat) performed four different efforts at constant intensity to exhaustion in order to determine CP and W’. The mechanical power values obtained were subsequently plotted with their corresponding time to exhaustion (limit time) for application of three mathematical models: power hyperbolic versus time limit (Hyp), linear power versus 1/time (P vs 1/t) and linear work versus time limit (Ԏ vs t). The 3MT test was carried out on the last day to determine end power (EP) and anaerobic capacity (WEP) using this methodology. EP value of 181.7 ± 52 was similar (p = 0.486) to 178.2 ± 61 (CP Hyp), 191.4 ± 55 (Ԏ vs t) and 188.3 ± 55 (P vs 1/t). WEP value of 17.9 ± 4.8 was not similar (p = 0.000) to 50.2 ± 15.3 (CP Hyp), 44.8 ± 8.7 (Ԏ vs t) and 45.5 ± 8.4 (P vs 1/t). Positive results (r = 0.78–0.98 and ICC = 0.88–0.99) of Pearson correlation and intraclass correlation (ICC–absolute agreement) were found for aerobic applications of conventional CP and 3MT. For anaerobic data, only the three models of conventional CP were correlated (r = 0.76–0.93); however, W’ from the three models was not correlated with WEP (r = 0.37–0.52). The results of this study suggest that 3MT in tethered running on non-motorized treadmills is a valid test for estimating CP aerobic parameters in a single day of application but not anaerobic parameters of W’. PMID:29444141

Hypermethylation of MST1 in IgG4-related autoimmune pancreatitis and rheumatoid arthritis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fukuhara, Takataro; Tomiyama, Takashi; Yasuda, Kaneki

The serine/threonine kinase Mst1 plays important roles in the control of immune cell trafficking, proliferation, and differentiation. Previously, we reported that Mst1 was required for thymocyte selection and regulatory T-cell functions, thereby the prevention of autoimmunity in mice. In humans, MST1 null mutations cause T-cell immunodeficiency and hypergammaglobulinemia with autoantibody production. RASSF5C(RAPL) is an activator of MST1 and it is frequently methylated in some tumors. Herein, we investigated methylation of the promoter regions of MST1 and RASSF5C(RAPL) in leukocytes from patients with IgG4-related autoimmune pancreatitis (AIP) and rheumatoid arthritis (RA). Increased number of CpG methylation in the 5′ region ofmore » MST1 was detected in AIP patients with extrapancreatic lesions, whereas AIP patients without extrapancreatic lesions were similar to controls. In RA patients, we detected a slight increased CpG methylation in MST1, although the overall number of methylation sites was lower than that of AIP patients with extrapancreatic lesions. There were no significant changes of the methylation levels of the CpG islands in the 5′ region of RASSF5C(RAPL) in leukocytes from AIP and RA patients. Consistently, we found a significantly down-regulated expression of MST1 in regulatory T cells of AIP patients. Our results suggest that the decreased expression of MST1 in regulatory T cells due to hypermethylation of the promoter contributes to the pathogenesis of IgG4-related AIP. - Highlights: • Mst1 controls immune cells trafficking, cell proliferation and differentiation. • Autoimmune pancreatitis (AIP) is an idiopathic pancreatitis affecting multiple organs. • Decreased MST1 expression and increased CpG methylation of promoter of MST1 in AIP. • Slight increased CpG methylation of MST1 in rheumatoid arthritis patients. • MST1 contributes pathogenesis of IgG4-related AIP.« less

In vitro anticancer evaluation of 5-fluorouracil lipid nanoparticles using B16F10 melanoma cell lines

NASA Astrophysics Data System (ADS)

Shenoy, Vikram S.; Gude, Rajiv P.; Murthy, Rayasa S. Ramachandra

2013-05-01

The present study is aimed to investigate the formulation and in vitro anticancer activities of solid lipid nanoparticles (SLNs) of 5-fluorouracil (5-FU) prepared using glyceryl monostearate (GMS) and cetyl palmitate (CP) by hot homogenization method. The lipids were selected based on the partition coefficient of 5-FU in lipids. The lipid nanoparticles were optimized for process and formulation parameters. The optimized nanoparticles were characterized for their zeta potential, morphology, release kinetics, and anticancer activity. Higher entrapments were achieved using a combination of emulsifiers. The zeta potential of the optimized CP and GMS SLN formulation were -8.26 and -9.35 mV, respectively. Both the optimized formulations were spherical. The in vitro release studies of SLNs of both the lipid carriers followed Peppas-Korsenmeyer equation when carried out at pH 3.5 and 7.4. The chemosensitivity assay carried out in B16F10 cell lines revealed that CP SLNs had better cytotoxicity than 5-FU solution and GMS SLNs at 48 h of incubation. Subtoxic concentration of 5-FU-loaded CP SLNs (0.12 μg/mL) possessed comparable antimigrational activity, colony inhibition activity, and cytopathic as that of 5-FU solution effects. The results indicated that encapsulating 5-FU in CP would be a promising delivery system for delivering 5-FU.

Neuropsychological profiles of children with cerebral palsy.

PubMed

Stadskleiv, Kristine; Jahnsen, Reidun; Andersen, Guro L; von Tetzchner, Stephen

2018-02-01

To explore factors contributing to variability in cognitive functioning in children with cerebral palsy (CP). A geographical cohort of 70 children with CP was assessed with tests of language comprehension, visual-spatial reasoning, attention, working memory, memory, and executive functioning. Mean age was 9;9 years (range 5;1-17;7), 54.3% were girls, and 50.0% had hemiplegic, 25.7% diplegic, 12.9% quadriplegic, and 11.4% dyskinetic CP. For the participants with severe motor impairments, assessments were adapted for gaze pointing. A cognitive quotient (CQ) was computed. Mean CQ was 78.5 (range 19-123). Gross motor functioning, epilepsy, and type of brain injury explained 35.5% of the variance in CQ (F = 10.643, p = .000). Twenty-four percent had an intellectual disability, most of them were children with quadriplegic CP. Verbal comprehension and perceptual reasoning scores did only differ for the 21% with an uneven profile, of whom two-thirds had challenges with perceptual reasoning.

An Icosidodecahedral Supramolecule Based on Pentaphosphaferrocene: From a Disordered Average Structure to Individual Isomers

PubMed Central

Heindl, Claudia; Peresypkina, Eugenia; Virovets, Alexander V.; Bushmarinov, Ivan S.; Medvedev, Michael G.; Krämer, Barbara; Dittrich, Birger

2017-01-01

Abstract Pentaphosphaferrocenes [CpRFe(η5‐P5)] (1) and CuI halides are excellent building blocks for the formation of discrete supramolecules. Herein, we demonstrate the potential of Cu(CF3SO3) for the construction of the novel 2D polymer [{Cp*Fe(μ4,η5:1:1:1‐P5)}{Cu(CF3SO3)}]n (2) and the unprecedented nanosphere (CH2Cl2)1.4@[{CpBnFe(η5‐P5)}12{Cu(CF3SO3)}19.6] (3). The supramolecule 3 has a unique scaffold beyond the fullerene topology, with 20 copper atoms statistically distributed over the 30 vertices of an icosidodecahedron. Combinatorics was used to interpret the average disordered structure of the supramolecules. In this case, only two pairs of enantiomers with D5 and D2 symmetry are possible for bidentate bridging coordination of the triflate ligands. DFT calculations showed that differences in the energies of the isomers are negligible. The benzyl ligands enhance the solubility of 3, enabling NMR‐spectroscopic and mass‐spectrometric investigations. PMID:28793182

Cognitive Profile in Young Icelandic Children with Cerebral Palsy

ERIC Educational Resources Information Center

Sigurdardottir, Solveig; Eiriksdottir, Audur; Gunnarsdottir, Eva; Meintema, Marrit; Arnadottir, Unnur; Vik, Torstein

2008-01-01

We describe the cognitive profile in a complete national cohort of children with cerebral palsy (CP). One hundred and twenty-seven Icelandic children (67 females, 60 males) with CP, born between 1985 and 2000 and assessed between the ages of 4 and 6 years 6 months (mean age 5y 5mo, SD 6mo), were included in the study. IQ was measured using the…

75 FR 67148 - New Postal Product

Federal Register 2010, 2011, 2012, 2013, 2014

2010-11-01

... POSTAL REGULATORY COMMISSION [Docket Nos. CP2011-5 Through CP2011-12; Order No. 557] New Postal Product AGENCY: Postal Regulatory Commission. ACTION: Notice. SUMMARY: The Commission is noticing a.... at 4. The Postal Service concludes that its filings demonstrate that each of the new GEPS 3 contracts...

50 CFR 660.160 - Catcher/processor (C/P) Coop Program.

Code of Federal Regulations, 2010 CFR

2010-10-01

... Coop Program, or the Shorebased IFQ Program. As determined necessary by the Regional Administrator... combination. [Reserved] (4) Appeals. [Reserved] (5) Fees. The Regional Administrator is authorized to charge... entry permit owner in the NMFS permit database. (ii) Qualifying criteria for C/P endorsement. In order...

Facilities Maintenance in the U.S. Navy

DTIC Science & Technology

1986-01-01

Row’a9IVI s..Nl,I I~de 14. 11111116104 It. safeI MeAI. 5,124 AN (:lgnd) JOHN SMITH I765 IIf Figure 111-1 Work Request is EMIROENCY/SERVICE WORK...Eliminate fire, health and active life of less than 3 years safety hazards o Infrequently or only partially o Patch and reinforce instead used of...safety or health hazards and to permit reactivation within the period prescribed under mobili- zation plans o Surplus facilities a Fliminate fire, safety

Reducing the CP content in broiler feeds: impact on animal performance, meat quality and nitrogen utilization.

PubMed

Belloir, P; Méda, B; Lambert, W; Corrent, E; Juin, H; Lessire, M; Tesseraud, S

2017-11-01

Reducing the dietary CP content is an efficient way to limit nitrogen excretion in broilers but, as reported in the literature, it often reduces performance, probably because of an inadequate provision in amino acids (AA). The aim of this study was to investigate the effect of decreasing the CP content in the diet on animal performance, meat quality and nitrogen utilization in growing-finishing broilers using an optimized dietary AA profile based on the ideal protein concept. Two experiments (1 and 2) were performed using 1-day-old PM3 Ross male broilers (1520 and 912 for experiments 1 and 2, respectively) using the minimum AA:Lys ratios proposed by Mack et al. with modifications for Thr and Arg. The digestible Thr (dThr): dLys ratio was increased from 63% to 68% and the dArg:dLys ratio was decreased from 112% to 108%. In experiment 1, the reduction of dietary CP from 19% to 15% (five treatments) did not alter feed intake or BW, but the feed conversion ratio was increased for the 16% and 15% CP diets (+2.4% and +3.6%, respectively), while in experiment 2 (three treatments: 19%, 17.5% and 16% CP) there was no effect of dietary CP on performance. In both experiments, dietary CP content did not affect breast meat yield. However, abdominal fat content (expressed as a percentage of BW) was increased by the decrease in CP content (up to +0.5 and +0.2 percentage point, in experiments 1 and 2, respectively). In experiment 2, meat quality traits responded to dietary CP content with a higher ultimate pH and lower lightness and drip loss values for the low CP diets. Nitrogen retention efficiency increased when reducing CP content in both experiments (+3.5 points/CP percentage point). The main consequence of this higher efficiency was a decrease in nitrogen excretion (-2.5 g N/kg BW gain) and volatilization (expressed as a percentage of excretion: -5 points/CP percentage point). In conclusion, this study demonstrates that with an adapted AA profile, it is possible to reduce dietary CP content to at least 17% in growing-finishing male broilers, without altering animal performance and meat quality. Such a feeding strategy could therefore help improving the sustainability of broiler production as it is an efficient way to reduce environmental burden associated with nitrogen excretion.

Morphological and functional changes of chronic pancreatitis in patients with dyspepsia: A prospective, observational, cross-sectional study.

PubMed

Lariño-Noia, José; de la Iglesia, Daniel; Iglesias-García, Julio; Macías, Fernando; Nieto, Laura; Bastón, Iria; Villalba, Carmen; Domínguez-Muñoz, J Enrique

2018-04-01

Whether chronic pancreatitis (CP) may present with dyspepsia is controversial. We aimed at evaluating the frequency and risk factors of changes of CP in patients presenting with epigastric pain syndrome (EPS)-like symptoms. A prospective, observational, cross-sectional study was carried out in patients with EPS-like symptoms. Patients underwent endoscopic ultrasound (EUS) evaluation of the pancreas, and changes of CP were defined as the presence of five or more EUS criteria of the disease. In patients with 3 or 4 EUS criteria, magnetic resonance dynamic evaluation of the pancreas (MRI/sMRCP) and endoscopic pancreatic function test (ePFT) were carried out to confirm or exclude the presence of changes of CP. A multivariate logistic regression analysis was performed to evaluate factors associated with CP findings, and results are shown as odds ratio (OR) and 95% confidence interval (CI). 213 patients were included. Changes of CP were confirmed by EUS (≥5 criteria) in 18 patients (8.4%). Thirty-four patients had 3-4 EUS criteria, and changes of CP were confirmed in 27 of them by MRI/sMRCP and ePFT (12.7%). Morphological and functional findings of CP were then present in 45 patients (21.1%). Male gender (OR 2.97; 95%CI 1.39-6.37) and alcohol and tobacco consumption (OR 6.56; 95%CI 1.97-21.85) were associated with the presence of changes of CP. Morphological and functional changes of CP are frequent in patients with EPS-like symptoms. Whether these pancreatic changes explain EPS-like symptoms requires further investigation. Copyright © 2018 IAP and EPC. Published by Elsevier B.V. All rights reserved.

Comparative analysis of blood and saliva expression profiles in chronic and refractory periodontitis patients.

PubMed

Zhang, Bin; Lin, Ting; He, Hong

2015-12-24

This study aimed to identify characteristic representative genes through a comparative analysis of gene expression profiles in the blood and saliva of chronic periodontitis (CP) and refractory periodontitis (RP) patients to provide new treatment strategies that may be helpful in the treatment of different forms of periodontitis. GSE43525 was downloaded from Gene Expression Omnibus. In the dataset, thirteen samples were from blood including 4 controls, 4 CP and 5 RP samples, and ten samples were from saliva including 3 controls, 4 CP and 3 RP samples. After comparing the CP and RP samples, differentially expressed genes (DEGs) between these two types of periodontitis in the blood and saliva samples were identified by an LIMMA package. Then, functional and pathway enrichment analyses were performed by DAVID and KOBAS, respectively. The significantly associated miRNAs in CP and RP were searched by WebGestalt. In total, 213 DEGs in CP and 45 DEGs in RP were identified. Functional enrichment showed that the DEGs of CP were mainly enriched in ribosome and regulation of apoptosis-related pathways in blood as well as saliva, while the DEGs of RP were significantly enriched in immune responses and response to organic substance-related pathways. Several miRNAs, such as miR-381 and miR-494, were identified as being closely associated with CP. In addition, CD24, EST1, MTSS1, ING3, CCND2 and SYNE2 might be potential targets for diagnosis and treatment of CP. The identified DEGs and miRNAs might be potential targets for the treatment of chronic and refractory periodontitis.

Nocardia globerula NHB-2 nitrilase catalysed biotransformation of 4-cyanopyridine to isonicotinic acid

PubMed Central

2012-01-01

Isonicotinic acid (INA) is an important pyridine derivative used in the manufacture of isoniazid (antituberculosatic drug) and other pharmaceutically important drugs. Nitrilase catalysed processes for the synthesis of pharmaceutically important acids from their corresponding nitriles are promising alternative over the cumbersome, hazardous, and energy demanding chemical processes. Nitrilase of Nocardia globerula NHB-2 (NitNHB2) is expressed in presence of isobutyronitrile in the growth medium (1.0% glucose, 0.5% peptone, 0.3% beef extract, and 0.1 % yeast extract, pH 7.5). NitNHB2 hydrolyses 4-cyanopyridine (4-CP) to INA without accumulation of isonicotinamide, which is common in the reaction catalysed via fungal nitrilases. The NitNHB2 suffers from substrate inhibition effect and hydrolysing activity up to 250 mM 4-CP was recorded. Complete conversion of 200 mM 4-CP to INA was achieved in 40 min using resting cell concentration corresponding to 10 U mL-1 nitrilase activity in the reaction. Substrate inhibition effect in the fed batch reaction (200 mM substrate feed/40min) led to formation of only 729 mM INA. In a fed batch reaction (100 mM 4-CP/20min), substrate inhibition effect was encountered after 7th feed and a total of 958 mM INA was produced in 400 min. The fed batch reaction scaled up to 1 L and 100% hydrolysis of 700 mM of 4-CP to INA at 35°C achieved in 140 min. The rate of INA production was 21.1 g h-1 mgDCW-1. This is the fastest biotransformation process ever reported for INA production with time and space productivity of 36 g L-1 h-1 using a bacterial nitrilase. PMID:22537922

Nationwide cross-sectional study of the impact of chronic pain on an individual's employment: relationship with the family and the social support.

PubMed

de Sola, Helena; Salazar, Alejandro; Dueñas, María; Ojeda, Begoña; Failde, Inmaculada

2016-12-23

To determine the prevalence and the factors related to sick leave and job loss among individuals suffering from chronic pain (CP), and to analyse specifically the effect of family and social support on the individual's employment. Observational cross-sectional study. Data were collected using structured computer-assisted telephone interviews between February and June 2011. A nationwide study of 1543 Spanish adults of working age (<65), 213 of whom suffered from CP (pain suffered at least 4 or 5 days a week during the past 3 months, according to the criteria of the International Association for the Study of Pain (IASP)). Information was collected regarding the individual's sociodemographic status, pain characteristics, healthcare use and satisfaction, limitations in daily activities, mood status, perception of the impact of pain on their families, and their satisfaction with the family and social support. To identify factors associated with sick leave and job loss among those suffering CP, 2 logistic regression models were generated. The prevalence of sick leave due to CP in the general Spanish population was 4.21% (95% CI 3.2% to 5.2%). Sick leave were more likely for individuals who considered their family were affected by their pain (OR=2.18), needed help to dressing and grooming (OR=2.98), taking medication (OR=2.18), had a shorter pain duration (OR=0.99) and higher educational level. The prevalence of job loss due to CP was 1.8% (95% CI 1.1% to 2.5%). It was related to feelings of sadness (OR=4.25), being unsatisfied with the care provided by health professionals (OR=2.60) and consulting a doctor more often due to CP (OR=1.09). CP is negatively associated with an individual's employment. This detrimental effect could be ameliorated if the factors related to sick leave and job loss provoked by CP are identified, especially those related to the effect of CP on the family and social environment. Published by the BMJ Publishing Group Limited. For permission to use (where not already granted under a licence) please go to http://www.bmj.com/company/products-services/rights-and-licensing/.

Bach2 repression mediates Th17 cell induced inflammation and associates with clinical features of advanced disease in chronic pancreatitis

PubMed Central

Sasikala, M; Ravikanth, VV; Murali Manohar, K; Deshpande, Neha; Singh, Sandhya; Pavan Kumar, P; Talukdar, R; Ghosh, Sudip; Aslam, Mohsin; Rao, GV; Pradeep, R; Reddy, D Nageshwar

2018-01-01

Objectives Altered immune homeostasis and involvement of T cells has been reported in chronic pancreatitis (CP). We evaluated the role of Bach2 (BTB and CNC homology basic leucine zipper transcription factor 2), a key regulator of immune homeostasis in the chronicity of CP. Methods Expression of Bach2 and T-cell transcription factors, enumeration of BACH2+/CD4+ T-lymphocytes were performed by qRT-PCR and flow cytometry respectively. Bach2silenced human CD4+ T-lymphocytes were exposed to CP tissue extract to assess T-cell lineage commitment. Aryl hydrocarbon receptor (Ahr) and Deubiquitinase enzyme A (DUBA/OTUD5gene) were evaluated as markers of persistent Th17 cell differentiation. Bach2 gene (exons) was sequenced to identify risk variants and functionally validated. Results Decrease in Bach2 (p < 0.0001) and increase (p < 0.001) in TBX21, RORC, Ahr, PRDM1, IL23R mRNA were noted in pancreatic tissues, while BACH2+/CD4+ T-lymphocytes were decreased (p < 0.01) in circulation and tissues. Exposure of Bach2 silenced CD4+ T-lymphocytes to CP tissue extract showed increased Ahr, decreased OTUD5, and enhanced Th17 cell differentiation. Sequencing of Bach2 gene revealed association of novel variant (rs9111 in 5′-UTR) with advanced disease and luciferase assay confirmed its role in Bach2 repression. Conclusion Bach2 repression mediates Th17 cell induced inflammation and rs9111-TT in individuals with primary genetic susceptibility to CP is associated with clinical features of advanced disease. PMID:29511557

Congenital cytomegalovirus is associated with severe forms of cerebral palsy and female sex in a retrospective population-based study.

PubMed

Smithers-Sheedy, Hayley; Raynes-Greenow, Camille; Badawi, Nadia; McIntyre, Sarah; Jones, Cheryl A

2014-09-01

Congenital cytomegalovirus (cCMV) infection can result in poor outcomes including cerebral palsy (CP). The aim of this study was to describe the incidence and comorbidities of CP reported to the Australian Cerebral Palsy Register (ACPR) as attributed to cCMV infection. This was a retrospective population-based study. Cases were drawn from Australian state CP registers with population level ascertainment, 1993 to 2003 (n=2265; 56.4% males, Gross Motor Function Classification System [GMFCS] ratings available for Victorian cases only: 70% GMFCS levels I to III and 30% GMFCS levels IV to V). Clinical data were extracted and cases with cCMV reported as a known cause were compared with cases where cCMV was not reported. Children with cCMV (n=34; 12 males, 22 females; mean [SD] gestational age, 36.4 wk [4.4], range 24-41 wk) accounted for 1.5% of CP cases; 2.9 per 100,000 live births, (95% confidence intervals 1.9-3.9). When compared with CP cases where cCMV was not reported, proportionally, more CP cases with cCMV were born to younger mothers (p<0.001), were female (64% vs 43%, p=0.014), had spastic quadriplegia (73% vs 21%, p<0.001), required wheeled mobility i.e. GMFCS IV or V (78% vs 28%, p<0.001), had epilepsy (70% vs 30%, p<0.001), deafness (40% vs 2%, p<0.001), functional blindness (20% vs 5%, p<0.001), and severe communication impairment (71% vs 25%, p<0.001). cCMV is an important potentially preventable cause of CP and is associated with severe disability and female sex in cases reported to the ACPR. Future studies utilising prospective sample collection for cCMV testing are needed to confirm these findings. © 2014 Mac Keith Press.

Objectively measured sedentary time in youth with cerebral palsy compared with age-, sex-, and season-matched youth who are developing typically: an explorative study.

PubMed

Obeid, Joyce; Balemans, Astrid C J; Noorduyn, Stephen G; Gorter, Jan Willem; Timmons, Brian W

2014-08-01

Children with cerebral palsy (CP) demonstrate reduced physical activity levels compared with children with typical development. Sedentary behavior, including the duration and frequency of sedentary bouts, has not yet been objectively examined in this population but may have clinical implications for the development of secondary health complications. The aim of this study was to identify time spent sedentary and frequency of breaks interrupting sedentary time in youth with CP compared with youth without CP. It was hypothesized that individuals with CP would spend more hours sedentary than their peers and take fewer breaks to interrupt sedentary time. This was a cross-sectional, prospective study. A convenience sample of 17 ambulatory children with CP (15 boys and 2 girls) (mean age=13.0 years, SD=2.2) and 17 age-, sex-, and season-matched youth who were developing typically (TD group) (mean age=12.9 years, SD=2.5) wore an accelerometer over a 7-day period. Sedentary time (in minutes) and number of breaks from sedentary time, corrected for monitoring and sedentary time, respectively, were examined. Differences between groups were determined with an independent-samples t test. Children with CP engaged in significantly more sedentary time (X̅=47.5 min/h, SD=4.9) compared with the TD group (X̅=43.6 min/h, SD=4.2), with significantly fewer breaks from sedentary time (CP group: X̅=179, SD=70; TD group: X̅=232 breaks/h sedentary, SD=61). The sample included only ambulatory youth with CP, classified as Gross Motor Function Classification System levels I to III. Sedentary time was higher in the CP group and was characterized by less frequent breaks compared with the TD group. Future research should examine the extent to which sedentary time is associated with cardiovascular and metabolic risk in youth with CP. © 2014 American Physical Therapy Association.

CpG ODN 1668 induce innate and adaptive immune responses in rock bream (Oplegnathus fasciatus) against rock bream iridovirus (RBIV) infection.

PubMed

Jung, Myung-Hwa; Jung, Sung-Ju

2017-10-01

Rock bream iridovirus (RBIV) causes severe mass mortalities in rock bream in Korea. CpG ODN 1668 showed promise as immunoprotective agents against RBIV infection in rock bream. In this study, we assessed innate/adaptive-related gene expression patterns in RBIV-infected rock bream with and without CpG ODN 1668 administration to determine important immune defense related factors that may affect fish survival. In the CpG ODN 1668+virus-injected group, virus copies were more than 7.4- to 790591-fold lower than in the virus-injected group at 4 d (8.79 × 10 4 and 6.58 × 10 5 /μl, respectively), 7 d (5.30 × 10 2 and 2.29 × 10 7 /μl, respectively) and 10 dpi (7.79 × 10 1 and 6.16 × 10 7 /μl, respectively). Furthermore, in the CpG ODN 1668+virus-injected group, significantly higher levels of MyD88 (6 h, 1 d, 4 d and 7 dpi), IL1β (1 d, 2 d and 7 dpi) and perforin/granzyme (1 dpi) expression were observed, whereas these genes were not significantly expressed in the virus-injected group at that time points. Mx, ISG15 and PKR were significantly highly expressed at 4 d and 7 dpi and reduced when low viral loads at 10 dpi in the CpG ODN 1668+virus-injected group. Conversely, in the virus-injected group, Mx, ISG15 and PKR expression were significantly higher than the control group until 10 dpi. However, MHC class I, CD8, Fas, Fas ligand and caspases (3, 8 and 9) expression levels showed no statistically significant differences between virus- and CpG ODN 1668+virus-injected group. In summary, CpG ODN 1668 administration in fish induces innate immune response or cell death pathway, which could be a major contributing factor to effective fish control over viral transcription on 4 d to 10 dpi. Expression of MyD88, IL1β, perforin and granzyme-related immune gene response is critical factor for inhibition of RBIV replication. Copyright © 2017 Elsevier Ltd. All rights reserved.

Binding of 2-[18F]fluoro-CP-118,954 to mouse acetylcholinesterase: microPET and ex vivo Cerenkov luminescence imaging studies.

PubMed

Kim, Dong Hyun; Choe, Yearn Seong; Choi, Joon Young; Lee, Kyung-Han; Kim, Byung-Tae

2011-05-01

Acetylcholinesterase (AChE) has been an important cholinergic factor for the diagnosis of Alzheimer's disease (AD), because of reduced AChE activity in the postmortem brains of AD patients. We previously developed 5,7-dihydro-3-(2-(1-(2-[(18)F]fluorobenzyl)-4-piperidinyl)ethyl)-6H-pyrrolo(3,2,f)-1,2-benzisoxazol-6-one (2-[(18)F]fluoro-CP-118,954) for in vivo studies of AChE in mice. In the present study, we automated the synthesis of 2-[(18)F]fluoro-CP-118,954 for the routine use and evaluated the radioligand by microPET and ex vivo Cerenkov luminescence imaging of mouse AChE. 4-[(18)F]Fluoro-donepezil, another AChE inhibitor, was used for comparison. Automated syntheses of 2-[(18)F]fluoro-CP-118,954 and 4-[(18)F]fluoro-donepezil resulted in high radiochemical yields (25-33% and 30-40%) and high specific activity (27.1-35.4 and 29.7-37.3 GBq/μmol). Brain microPET images of two ICR mice injected with 2-[(18)F]fluoro-CP-118,954 demonstrated high uptake in the striatum (ROI analysis: 5.1 %ID/g for the first 30 min and 4.1 %ID/g for another 30 min), and a blocking study with injection of CP-118,954 into one of the mice at 30 min after radioligand injection led to complete blocking of radioligand uptake in the striatum (ROI analysis: 1.9 %ID/g), whereas (18)F-labeled donepezil did not show specific uptake in the striatum. In another set of experiments, the brain tissues (striatum, parietal cortex, frontal cortex and cerebellum) were excised after brain microPET/CT imaging of mouse injected with 2-[(18)F]fluoro-CP-118,954, and a high striatal uptake was also detected in ex vivo optical and microPET images (ROI analysis: 1.4 %ID/g) and in γ-counting data (2.1 %ID/g at 50 min post-injection) of the brain tissues. Taken together, these results demonstrated that 2-[(18)F]fluoro-CP-118,954 specifically binds to AChE in mouse brains. Copyright © 2011 Elsevier Inc. All rights reserved.

Selection bias in genetic-epidemiological studies of cleft lip and palate

DOE Office of Scientific and Technical Information (OSTI.GOV)

Christensen, K.; Holm, N.V.; Kock, K.

1992-09-01

The possible impact of selection bias in genetic and epidemiological studies of cleft lip and palate was studied, using three nationwide ascertainment sources and an autopsy study in a 10% sample of the Danish population. A total of 670 cases were identified. Two national record systems, when used together, were found suitable for ascertaining facial cleft in live births. More than 95% ascertainment was obtained by means of surgical files for cleft lip (with or without cleft palate) without associated malformations/syndromes. However, surgical files could be a poor source for studying isolated cleft palate (CP) (only a 60% and biasedmore » ascertainment), and they cannot be used to study the prevalence of associated malformations or syndromes in facial cleft cases. The male:female ratio was 0.88 in surgically treated cases of CP and was 1.5 in nonoperated CP cases, making the overall sex ratio for CP 1.1 (95% confidence limits 0.86-1.4) The sex ratio for CP without associated malformation was 1.1 (95% confidence limits 0.84-1.6). One of the major test criteria in CP multifactorial threshold models (higher CP liability among male CP relatives) must be reconsidered, if other investigations confirm that a CP sex-ratio reversal to male predominance occurs when high ascertainment is achieved. 24 refs., 1 fig., 4 tabs.« less

Early alterations in glycemic control and pancreatic endocrine function in non-diabetic patients with chronic pancreatitis

PubMed Central

Lundberg, Rachel; Beilman, Gregory J.; Dunn, Ty B.; Pruett, Tim L.; Freeman, Martin L.; Ptacek, Peggy E.; Berry, K. Louise; Robertson, R. Paul; Moran, Antoinette; Bellin, Melena D.

2015-01-01

Objectives Diabetes mellitus (DM) is a frequent consequence of chronic pancreatitis (CP). Little is known about pancreatic endocrine function before the development of DM in CP, particularly in females, or those without calcific and/or alcoholic pancreatitis. Methods Twenty-five non-diabetic adult CP patients (19 female, age 34.2 ± 2.4 yrs) were compared to 25 healthy controls matched for age, gender, and BMI. Subjects underwent frequent sample intravenous glucose tolerance testing (FSIVGTT) and mixed meal tolerance testing (MMTT). Results Mean fasting glucose was higher in CP patients (89.5 ±2.3 mg/dL) than in controls (84.4 ±1.2 mg/dL, p=0.04). On MMTT, CP patients had a higher area under the curve (AUC) glucose and AUC glucagon compared to controls (p≤0.01). AUC C-peptide was equivalent (p=0.6) but stimulated C-peptide at 30 minutes was lower in CP patients (p=0.04). Mean insulin sensitivity index calculated from the FSIVGTT was lower in CP group, indicating reduced insulin sensitivity (p≤0.01). Disposition index (insulin secretion adjusted for insulin sensitivity on FSIVGTT) was lower in CP patients (p=0.01). Conclusions CP patients had higher fasting and MMTT glucose levels, without a compensatory increase in insulin secretion suggesting subtle early islet dysfunction. Our cohort had relative hyperglucagonemia and were less insulin sensitive than controls. PMID:26918872

First Observation of CP Violation in B[over ¯]^{0}→D_{CP}^{(*)}h^{0} Decays by a Combined Time-Dependent Analysis of BABAR and Belle Data.

PubMed

Abdesselam, A; Adachi, I; Adametz, A; Adye, T; Ahmed, H; Aihara, H; Akar, S; Alam, M S; Albert, J; Al Said, S; Andreassen, R; Angelini, C; Anulli, F; Arinstein, K; Arnaud, N; Asner, D M; Aston, D; Aulchenko, V; Aushev, T; Ayad, R; Babu, V; Badhrees, I; Bahinipati, S; Bakich, A M; Band, H R; Banerjee, Sw; Barberio, E; Bard, D J; Barlow, R J; Batignani, G; Beaulieu, A; Bellis, M; Ben-Haim, E; Bernard, D; Bernlochner, F U; Bettarini, S; Bettoni, D; Bevan, A J; Bhardwaj, V; Bhuyan, B; Bianchi, F; Biasini, M; Biswal, J; Blinov, V E; Bloom, P C; Bobrov, A; Bomben, M; Bondar, A; Bonneaud, G R; Bonvicini, G; Bozek, A; Bozzi, C; Bračko, M; Briand, H; Browder, T E; Brown, D N; Brown, D N; Bünger, C; Burchat, P R; Buzykaev, A R; Calabrese, R; Calcaterra, A; Calderini, G; Carpinelli, M; Cartaro, C; Casarosa, G; Cenci, R; Červenkov, D; Chang, P; Chao, D S; Chauveau, J; Cheaib, R; Chekelian, V; Chen, A; Chen, C; Cheng, C H; Cheon, B G; Chilikin, K; Chistov, R; Cho, K; Chobanova, V; Choi, H H F; Choi, S-K; Chrzaszcz, M; Cibinetto, G; Cinabro, D; Cochran, J; Coleman, J P; Contri, R; Convery, M R; Cowan, G; Cowan, R; Cremaldi, L; Dalseno, J; Dasu, S; Davier, M; Davis, C L; De Mori, F; De Nardo, G; Denig, A G; Derkach, D; de Sangro, R; Dey, B; Di Lodovico, F; Dingfelder, J; Dittrich, S; Doležal, Z; Dorfan, J; Drásal, Z; Drutskoy, A; Druzhinin, V P; Dubois-Felsmann, G P; Dunwoodie, W; Dutta, D; Ebert, M; Echenard, B; Eidelman, S; Eigen, G; Eisner, A M; Emery, S; Ernst, J A; Faccini, R; Farhat, H; Fast, J E; Feindt, M; Ferber, T; Ferrarotto, F; Ferroni, F; Field, R C; Filippi, A; Finocchiaro, G; Fioravanti, E; Flood, K T; Ford, W T; Forti, F; Franco Sevilla, M; Fritsch, M; Fry, J R; Fulsom, B G; Gabathuler, E; Gabyshev, N; Gamba, D; Garmash, A; Gary, J W; Garzia, I; Gaspero, M; Gaur, V; Gaz, A; Gershon, T J; Getzkow, D; Gillard, R; Li Gioi, L; Giorgi, M A; Glattauer, R; Godang, R; Goh, Y M; Goldenzweig, P; Golob, B; Golubev, V B; Gorodeisky, R; Gradl, W; Graham, M T; Grauges, E; Griessinger, K; Gritsan, A V; Grosdidier, G; Grünberg, O; Guttman, N; Haba, J; Hafner, A; Hamilton, B; Hara, T; Harrison, P F; Hast, C; Hayasaka, K; Hayashii, H; Hearty, C; He, X H; Hess, M; Hitlin, D G; Hong, T M; Honscheid, K; Hou, W-S; Hsiung, Y B; Huard, Z; Hutchcroft, D E; Iijima, T; Inguglia, G; Innes, W R; Ishikawa, A; Itoh, R; Iwasaki, Y; Izen, J M; Jaegle, I; Jawahery, A; Jessop, C P; Joffe, D; Joo, K K; Julius, T; Kang, K H; Kass, R; Kawasaki, T; Kerth, L T; Khan, A; Kiesling, C; Kim, D Y; Kim, J B; Kim, J H; Kim, K T; Kim, P; Kim, S H; Kim, Y J; King, G J; Kinoshita, K; Ko, B R; Koch, H; Kodyš, P; Kolomensky, Yu G; Korpar, S; Kovalskyi, D; Kowalewski, R; Kravchenko, E A; Križan, P; Krokovny, P; Kuhr, T; Kumar, R; Kuzmin, A; Kwon, Y-J; Lacker, H M; Lafferty, G D; Lanceri, L; Lange, D J; Lankford, A J; Latham, T E; Leddig, T; Le Diberder, F; Lee, D H; Lee, I S; Lee, M J; Lees, J P; Leith, D W G S; Leruste, Ph; Lewczuk, M J; Lewis, P; Libby, J; Lockman, W S; Long, O; Lopes Pegna, D; LoSecco, J M; Lou, X C; Lueck, T; Luitz, S; Lukin, P; Luppi, E; Lusiani, A; Luth, V; Lutz, A M; Lynch, G; MacFarlane, D B; Malaescu, B; Mallik, U; Manoni, E; Marchiori, G; Margoni, M; Martellotti, S; Martinez-Vidal, F; Masuda, M; Mattison, T S; Matvienko, D; McKenna, J A; Meadows, B T; Miyabayashi, K; Miyashita, T S; Miyata, H; Mizuk, R; Mohanty, G B; Moll, A; Monge, M R; Moon, H K; Morandin, M; Muller, D R; Mussa, R; Nakano, E; Nakazawa, H; Nakao, M; Nanut, T; Nayak, M; Neal, H; Neri, N; Nisar, N K; Nishida, S; Nugent, I M; Oberhof, B; Ocariz, J; Ogawa, S; Okuno, S; Olaiya, E O; Olsen, J; Ongmongkolkul, P; Onorato, G; Onuchin, A P; Onuki, Y; Ostrowicz, W; Oyanguren, A; Pakhlova, G; Pakhlov, P; Palano, A; Pal, B; Palombo, F; Pan, Y; Panduro Vazquez, W; Paoloni, E; Park, C W; Park, H; Passaggio, S; Patel, P M; Patrignani, C; Patteri, P; Payne, D J; Pedlar, T K; Peimer, D R; Peruzzi, I M; Pesántez, L; Pestotnik, R; Petrič, M; Piccolo, M; Piemontese, L; Piilonen, L E; Pilloni, A; Piredda, G; Playfer, S; Poireau, V; Porter, F C; Posocco, M; Prasad, V; Prell, S; Prepost, R; Puccio, E M T; Pulliam, T; Purohit, M V; Pushpawela, B G; Rama, M; Randle-Conde, A; Ratcliff, B N; Raven, G; Ribežl, E; Richman, J D; Ritchie, J L; Rizzo, G; Roberts, D A; Robertson, S H; Röhrken, M; Roney, J M; Roodman, A; Rossi, A; Rostomyan, A; Rotondo, M; Roudeau, P; Sacco, R; Sakai, Y; Sandilya, S; Santelj, L; Santoro, V; Sanuki, T; Sato, Y; Savinov, V; Schindler, R H; Schneider, O; Schnell, G; Schroeder, T; Schubert, K R; Schumm, B A; Schwanda, C; Schwartz, A J; Schwitters, R F; Sciacca, C; Seiden, A; Sekula, S J; Senyo, K; Seon, O; Serednyakov, S I; Sevior, M E; Shapkin, M; Shebalin, V; Shen, C P; Shibata, T-A; Shiu, J-G; Simard, M; Simi, G; Simon, F; Simonetto, F; Skovpen, Yu I; Smith, A J S; Smith, J G; Snyder, A; So, R Y; Sobie, R J; Soffer, A; Sohn, Y-S; Sokoloff, M D; Sokolov, A; Solodov, E P; Solovieva, E; Spaan, B; Spanier, S M; Starič, M; Stocchi, A; Stroili, R; Stugu, B; Su, D; Sullivan, M K; Sumihama, M; Sumisawa, K; Sumiyoshi, T; Summers, D J; Sun, L; Tamponi, U; Taras, P; Tasneem, N; Teramoto, Y; Tisserand, V; Todyshev, K Yu; Toki, W H; Touramanis, C; Trabelsi, K; Tsuboyama, T; Uchida, M; Uglov, T; Unno, Y; Uno, S; Usov, Y; Uwer, U; Vahsen, S E; Van Hulse, C; Vanhoefer, P; Varner, G; Vasseur, G; Va'vra, J; Verderi, M; Vinokurova, A; Vitale, L; Vorobyev, V; Voß, C; Wagner, M N; Wagner, S R; Waldi, R; Walsh, J J; Wang, C H; Wang, M-Z; Wang, P; Watanabe, Y; West, C A; Williams, K M; Wilson, F F; Wilson, J R; Wisniewski, W J; Won, E; Wormser, G; Wright, D M; Wu, S L; Wulsin, H W; Yamamoto, H; Yamaoka, J; Yashchenko, S; Yuan, C Z; Yusa, Y; Zallo, A; Zhang, C C; Zhang, Z P; Zhilich, V; Zhulanov, V; Zupanc, A

2015-09-18

We report a measurement of the time-dependent CP asymmetry of B[over ¯]^{0}→D_{CP}^{(*)}h^{0} decays, where the light neutral hadron h^{0} is a π^{0}, η, or ω meson, and the neutral D meson is reconstructed in the CP eigenstates K^{+}K^{-}, K_{S}^{0}π^{0}, or K_{S}^{0}ω. The measurement is performed combining the final data samples collected at the ϒ(4S) resonance by the BABAR and Belle experiments at the asymmetric-energy B factories PEP-II at SLAC and KEKB at KEK, respectively. The data samples contain (471±3)×10^{6} BB[over ¯] pairs recorded by the BABAR detector and (772±11)×10^{6} BB[over ¯] pairs recorded by the Belle detector. We measure the CP asymmetry parameters -η_{f}S=+0.66±0.10(stat)±0.06(syst) and C=-0.02±0.07(stat)±0.03(syst). These results correspond to the first observation of CP violation in B[over ¯]^{0}→D_{CP}^{(*)}h^{0} decays. The hypothesis of no mixing-induced CP violation is excluded in these decays at the level of 5.4 standard deviations.

Process development and modeling of fluidized-bed reactor with coimmobilized biocatalyst for fuel ethanol production

NASA Astrophysics Data System (ADS)

Sun, May Yongmei

This research focuses on two steps of commercial fuel ethanol production processes: the hydrolysis starch process and the fermentation process. The goal of this research is to evaluate the performance of co-immobilized biocatalysts in a fluidized bed reactor with emphasis on economic and engineering aspects and to develop a predictive mathematical model for this system. The productivity of an FBR is higher than productivity of a traditional batch reactor or CSTR. Fluidized beds offer great advantages over packed beds for immobilized cells when small particles are used or when the reactant feed contains suspended solids. Plugging problems, excessive pressure drops (and thus attrition), or crushing risks may be avoided. No mechanical stirring is required as mixing occurs due to the natural turbulence in the fluidized process. Both enzyme and microorganism are immobilized in one catalyst bead which is called co-immobilization. Inside this biocatalyst matrix, starch is hydrolyzed by the enzyme glucoamylase to form glucose and then converted to ethanol and carbon dioxide by microorganisms. Two biocatalysts were evaluated: (1) co-immobilized yeast strain Saccharomyces cerevisiae and glucoamylase. (2) co-immobilized Zymomonas mobilis and glucoamylase. A co-immobilized biocatalyst accomplishes the simultaneous saccharification and fermentation (SSF process). When compared to a two-step process involving separate saccharification and fermentation stages, the SSF process has productivity values twice that given by the pre-saccharified process when the time required for pre-saccharification (15--25 h) was taken into account. The SSF process should also save capital cost. The information about productivity, fermentation yield, concentration profiles along the bed, ethanol inhibition, et al., was obtained from the experimental data. For the yeast system, experimental results showed that: no apparent decrease of productivity occurred after two and half months, the productivity was 25--44g/L-hr (based on reactor volume), the average yield was 0.45 g ethanol/g starch, the biocatalyst retained physical integrity and contamination did not affect fermentation. For the Z. mobilis system the maximum volumetric productivity was 38 g ethanol/L-h, the average yield was 0.51 g ethanol/g starch and the FBR was successfully operated for almost one month. In order to develop, scale-up and economically evaluate this system more efficiently, a predictive mathematical model that is based on fundamental principles was developed and verified. This model includes kinetics of reactions, transport phenomena of the reactant and product by diffusion within the biocatalyst bead, and the hydrodynamics of the three phase fluidized bed. The co-immobilized biocatalyst involves a consecutive reaction mechanism The mathematical descriptions of the effectiveness factors of reactant and the intermediate product were developed. Hydrodynamic literature correlations were used to develop the dispersion coefficient and gas, liquid, and solid holdup. The solutions of coupled non-linear second order equations for biocatalyst bead and reactor together with the boundary conditions were solved numerically. This model gives considerable information about the system, such as concentration profiles inside both the beads and column, flow rate and feed concentration influences on productivity and phase hold up, and the influence of enzyme and cell mass loading in the catalyst. This model is generic in nature such that it can be easily applied to a diverse set of applications and operating conditions.

Distinctive Klf4 mutants determine preference for DNA methylation status

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hashimoto, Hideharu; Wang, Dongxue; Steves, Alyse N.

Reprogramming of mammalian genome methylation is critically important but poorly understood. Klf4, a transcription factor directing reprogramming, contains a DNA binding domain with three consecutive C2H2 zinc fingers. Klf4 recognizes CpG or TpG within a specific sequence. Mouse Klf4 DNA binding domain has roughly equal affinity for methylated CpG or TpG, and slightly lower affinity for unmodified CpG. The structural basis for this key preference is unclear, though the side chain of Glu446 is known to contact the methyl group of 5-methylcytosine (5mC) or thymine (5-methyluracil). We examined the role of Glu446 by mutagenesis. Substituting Glu446 with aspartate (E446D) resultedmore » in preference for unmodified cytosine, due to decreased affinity for 5mC. In contrast, substituting Glu446 with proline (E446P) increased affinity for 5mC by two orders of magnitude. Structural analysis revealed hydrophobic interaction between the proline's aliphatic cyclic structure and the 5-methyl group of the pyrimidine (5mC or T). As in wild-type Klf4 (E446), the proline at position 446 does not interact directly with either the 5mC N4 nitrogen or the thymine O4 oxygen. In contrast, the unmethylated cytosine's exocyclic N4 amino group (NH2) and its ring carbon C5 atom hydrogen bond directly with the aspartate carboxylate of the E446D variant. Both of these interactions would provide a preference for cytosine over thymine, and the latter one could explain the E446D preference for unmethylated cytosine. Finally, we evaluated the ability of these Klf4 mutants to regulate transcription of methylated and unmethylated promoters in a luciferase reporter assay.« less

Gene silencing of Nox4 by CpG island methylation during hepatocarcinogenesis in rats

PubMed Central

López-Álvarez, Guadalupe S.; Wojdacz, Tomasz K.; García-Cuellar, Claudia M.; Monroy-Ramírez, Hugo C.; Rodríguez-Segura, Miguel A.; Pacheco-Rivera, Ruth A.; Valencia-Antúnez, Carlos A.; Cervantes-Anaya, Nancy; Soto-Reyes, Ernesto; Vásquez-Garzón, Verónica R.; Sánchez-Pérez, Yesennia; Villa-Treviño, Saúl

2017-01-01

ABSTRACT The association between the downregulation of genes and DNA methylation in their CpG islands has been extensively studied as a mechanism that favors carcinogenesis. The objective of this study was to analyze the methylation of a set of genes selected based on their microarray expression profiles during the process of hepatocarcinogenesis. Rats were euthanized at: 24 h, 7, 11, 16 and 30 days and 5, 9, 12 and 18 months post-treatment. We evaluated the methylation status in the CpG islands of four deregulated genes (Casp3, Cldn1, Pex11a and Nox4) using methylation-sensitive high-resolution melting technology for the samples obtained from different stages of hepatocarcinogenesis. We did not observe methylation in Casp3, Cldn1 or Pex11a. However, Nox4 exhibited altered methylation patterns, reaching a maximum of 10%, even during the early stages of hepatocarcinogenesis. We observed downregulation of mRNA and protein of Nox4 (97.5% and 40%, respectively) after the first carcinogenic stimulus relative to the untreated samples. Our results suggest that Nox4 downregulation is associated with DNA methylation of the CpG island in its promoter. We propose that methylation is a mechanism that can silence the expression of Nox4, which could contribute to the acquisition of neoplastic characteristics during hepatocarcinogenesis in rats. PMID:27895046

Colossal Dielectric Behavior of Ga+Nb Co-Doped Rutile TiO2.

PubMed

Dong, Wen; Hu, Wanbiao; Berlie, Adam; Lau, Kenny; Chen, Hua; Withers, Ray L; Liu, Yun

2015-11-18

Stimulated by the excellent colossal permittivity (CP) behavior achieved in In+Nb co-doped rutile TiO2, in this work we investigate the CP behavior of Ga and Nb co-doped rutile TiO2, i.e., (Ga(0.5)Nb(0.5))(x)Ti(1-x)O2, where Ga(3+) is from the same group as In(3+) but with a much smaller ionic radius. Colossal permittivity of up to 10(4)-10(5) with an acceptably low dielectric loss (tan δ = 0.05-0.1) over broad frequency/temperature ranges is obtained at x = 0.5% after systematic synthesis optimizations. Systematic structural, defect, and dielectric characterizations suggest that multiple polarization mechanisms exist in this system: defect dipoles at low temperature (∼10-40 K), polaronlike electron hopping/transport at higher temperatures, and a surface barrier layer capacitor effect. Together these mechanisms contribute to the overall dielectric properties, especially apparent observed CP. We believe that this work provides comprehensive guidance for the design of new CP materials.

Venenivibrio stagnispumantis gen. nov., sp. nov., a thermophilic hydrogen-oxidizing bacterium isolated from Champagne Pool, Waiotapu, New Zealand.

PubMed

Hetzer, Adrian; McDonald, Ian R; Morgan, Hugh W

2008-02-01

A novel thermophilic, hydrogen-oxidizing bacterium, designated strain CP.B2(T), was isolated from a terrestrial hot spring in Waiotapu, New Zealand. Cells were motile, slightly rod-shaped, non-spore-forming and Gram-negative. Isolate CP.B2(T) was an obligate chemolithotroph, growing by utilizing H(2) as electron donor and O(2) as corresponding electron acceptor. Elemental sulfur (S(0)) or thiosulfate ( ) was essential for growth. Microbial growth occurred under microaerophilic conditions in 1.0-10.0 % (v/v) O(2) [optimum 4-8 % (v/v) O(2)], between 45 and 75 degrees C (optimum 70 degrees C) and at pH values of 4.8-5.8 (optimum pH 5.4). The DNA G+C content was 29.3 mol%. 16S rRNA gene sequence analysis demonstrated that strain CP.B2(T) belonged to the order Aquificales, with a close phylogenetic relationship to Sulfurihydrogenibium azorense (94 % sequence similarity to the type strain). However, genotypic and metabolic characteristics differentiated the novel isolate from previously described genera of the Aquificales. Therefore, CP.B2(T) represents a novel species in a new genus, for which the name Venenivibrio stagnispumantis gen. nov., sp. nov. is proposed. The type strain of Venenivibrio stagnispumantis is CP.B2(T) (=JCM 14244(T) =DSM 18763(T)).

A supramolecular Tröger's base derived coordination zinc polymer for fluorescent sensing of phenolic-nitroaromatic explosives in water.

PubMed

Shanmugaraju, Sankarasekaran; Dabadie, Charlyne; Byrne, Kevin; Savyasachi, Aramballi J; Umadevi, Deivasigamani; Schmitt, Wolfgang; Kitchen, Jonathan A; Gunnlaugsson, Thorfinnur

2017-02-01

A V-Shaped 4-amino-1,8-napthalimide derived tetracarboxylic acid linker ( L ; bis-[ N -(1,3-benzenedicarboxylic acid)]-9,18-methano-1,8-naphthalimide-[ b , f ][1,5]diazocine) comprising the Tröger's base (TB) structural motif was rationally designed and synthesised to access a nitrogen-rich fluorescent supramolecular coordination polymer. By adopting the straight forward precipitation method, a new luminescent nanoscale Zn(ii) coordination polymer ( TB-Zn-CP ) was synthesized in quantitative yield using Zn(OAc) 2 ·2H 2 O and tetraacid linker L (1 : 0.5) in DMF at room temperature. The phase-purity of as-synthesised TB-Zn-CP was confirmed by X-ray powder diffraction analysis, infra-red spectroscopy, and elemental analysis. Thermogravimetric analysis suggests that TB-Zn-CP is thermally stable up to 330 °C and the morphological features of TB-Zn-CP was analysed by SEM and AFM techniques. The N 2 adsorption isotherm of thermally activated TB-Zn-CP at 77 K revealed a type-II reversible adsorption isotherm and the calculated Brunauer-Emmett-Teller (BET) surface area was found to be 72 m 2 g -1 . Furthermore, TB-Zn-CP displayed an excellent CO 2 uptake capacity of 76 mg g -1 at 273 K and good adsorption selectivity for CO 2 over N 2 and H 2 . The aqueous suspension of as-synthesized TB-Zn-CP showed strong green fluorescence ( λ max = 520 nm) characteristics due to the internal-charge transfer (ICT) transition and was used as a fluorescent sensor for the discriminative sensing of nitroaromatic explosives. The aqueous suspension of TB-Zn-CP showed the largest quenching responses with high selectivity for phenolic-nitroaromatics (4-NP, 2,4-DNP and PA) even in the concurrent presence of other potentially competing nitroaromatic analytes. The fluorescence titration studies also provide evidence that TB-Zn-CP detects picric acid as low as the parts per billion (26.3 ppb) range. Furthermore, the observed fluorescence quenching responses of TB-Zn-CP towards picric acid were highly reversible. The highly selective fluorescence quenching responses including the reversible detection efficiency make the nanoscale coordination polymer TB-Zn-CP a potential material for the discriminative fluorescent sensing of nitroaromatic explosives.

Sigma decomposition: the CP-odd Lagrangian

NASA Astrophysics Data System (ADS)

Hierro, I. M.; Merlo, L.; Rigolin, S.

2016-04-01

In Alonso et al., JHEP 12 (2014) 034, the CP-even sector of the effective chiral Lagrangian for a generic composite Higgs model with a symmetric coset has been constructed, up to four momenta. In this paper, the CP-odd couplings are studied within the same context. If only the Standard Model bosonic sources of custodial symmetry breaking are considered, then at most six independent operators form a basis. One of them is the weak- θ term linked to non-perturbative sources of CP violation, while the others describe CP-odd perturbative couplings between the Standard Model gauge bosons and an Higgs-like scalar belonging to the Goldstone boson sector. The procedure is then applied to three distinct exemplifying frameworks: the original SU(5)/SO(5) Georgi-Kaplan model, the minimal custodial-preserving SO(5)/SO(4) model and the minimal SU(3)/(SU(2) × U(1)) model, which intrinsically breaks custodial symmetry. Moreover, the projection of the high-energy electroweak effective theory to the low-energy chiral effective Lagrangian for a dynamical Higgs is performed, uncovering strong relations between the operator coefficients and pinpointing the differences with the elementary Higgs scenario.

Transmembrane delivery of anticancer drugs through self-assembly of cyclic peptide nanotubes

NASA Astrophysics Data System (ADS)

Chen, Jian; Zhang, Bei; Xia, Fei; Xie, Yunchang; Jiang, Sifan; Su, Rui; Lu, Yi; Wu, Wei

2016-03-01

Breaking the natural barriers of cell membranes achieves fast entry of therapeutics, which leads to enhanced efficacy and helps overcome multiple drug resistance. Herein, transmembrane delivery of a series of small molecule anticancer drugs was achieved by the construction of artificial transmembrane nanochannels formed by self-assembly of cyclic peptide (cyclo[Gln-(d-Leu-Trp)4-d-Leu], CP) nanotubes (CPNTs) in the lipid bilayers. Our in vitro study in liposomes indicated that the transport of molecules with sizes smaller than 1.0 nm, which is the internal diameter of the CPNTs, could be significantly enhanced by CPNTs in a size-selective and dose-dependent manner. Facilitated uptake of 5-fluorouracil (5-FU) was also confirmed in the BEL7402 cell line. On the contrary, CPs could facilitate neither the transport across liposomal membranes nor the uptake by cell lines of cytarabine, a counterevidence drug with a size of 1.1 nm. CPs had a very weak anticancer efficacy, but could significantly reduce the IC50 of 5-FU in BEL7402, HeLa and S180 cell lines. Analysis by a q test revealed that a combination of 5-FU and CP had a synergistic effect in BEL7402 at all CP levels, in S180 at CP levels higher than 64 μg mL-1, but not in HeLa, where an additive effect was observed. Temporarily, intratumoral injection is believed to be the best way for CP administration. In vivo imaging using 125I radio-labelled CP confirmed that CPNPTs were completely localized in the tumor tissues, and translocation to other tissues was negligible. In vivo anticancer efficacy was studied in the grafted S180 solid tumor model in mice, and the results indicated that tumor growth was greatly inhibited by the combinatory use of 5-FU and CP, and a synergistic effect was observed at CP doses of 0.25 mg per kg bw. It is concluded that facilitated transmembrane delivery of anticancer drugs with sizes smaller than 1.0 nm was achieved, and the synergistic anticancer effect was confirmed both in cell lines and in vivo through the combinatory use of 5-FU and CP.Breaking the natural barriers of cell membranes achieves fast entry of therapeutics, which leads to enhanced efficacy and helps overcome multiple drug resistance. Herein, transmembrane delivery of a series of small molecule anticancer drugs was achieved by the construction of artificial transmembrane nanochannels formed by self-assembly of cyclic peptide (cyclo[Gln-(d-Leu-Trp)4-d-Leu], CP) nanotubes (CPNTs) in the lipid bilayers. Our in vitro study in liposomes indicated that the transport of molecules with sizes smaller than 1.0 nm, which is the internal diameter of the CPNTs, could be significantly enhanced by CPNTs in a size-selective and dose-dependent manner. Facilitated uptake of 5-fluorouracil (5-FU) was also confirmed in the BEL7402 cell line. On the contrary, CPs could facilitate neither the transport across liposomal membranes nor the uptake by cell lines of cytarabine, a counterevidence drug with a size of 1.1 nm. CPs had a very weak anticancer efficacy, but could significantly reduce the IC50 of 5-FU in BEL7402, HeLa and S180 cell lines. Analysis by a q test revealed that a combination of 5-FU and CP had a synergistic effect in BEL7402 at all CP levels, in S180 at CP levels higher than 64 μg mL-1, but not in HeLa, where an additive effect was observed. Temporarily, intratumoral injection is believed to be the best way for CP administration. In vivo imaging using 125I radio-labelled CP confirmed that CPNPTs were completely localized in the tumor tissues, and translocation to other tissues was negligible. In vivo anticancer efficacy was studied in the grafted S180 solid tumor model in mice, and the results indicated that tumor growth was greatly inhibited by the combinatory use of 5-FU and CP, and a synergistic effect was observed at CP doses of 0.25 mg per kg bw. It is concluded that facilitated transmembrane delivery of anticancer drugs with sizes smaller than 1.0 nm was achieved, and the synergistic anticancer effect was confirmed both in cell lines and in vivo through the combinatory use of 5-FU and CP. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr06804e

Giant Rugby Ball [{CpBnFe(η5-P5)}24Cu96Br96] Derived from Pentaphosphaferrocene and CuBr2

PubMed Central

2015-01-01

The self-assembly of [CpBnFe(η5-P5)] (CpBn = η5-C5(CH2Ph)5) with CuBr2 leads to the formation of an unprecedented rugby ball-shaped supramolecule consisting of 24 units of the pentaphosphaferrocene and an extended CuBr framework, which does not follow the fullerene topology. The resulting scaffold of 312 noncarbon atoms reveals three different coordination modes of the cyclo-P5 ligand including a novel π-coordination. The outer dimensions of 3.7 × 4.6 nm of the sphere approach the range of the size of proteins. With a value of 32.1 nm3, it is 62 times larger in volume than a C60 molecule. Surprisingly, this giant rugby ball is also slightly soluble in CH2Cl2. PMID:26280785

A rechargeable lithium battery employing cobalt chevrel-phase compound as the cathode

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yomaguchi, S.; Uchida, T.; Wakihara, M.

This paper reports on the single-phase region of cobalt Chevrel-phase compound (Co{sub y}Mo{sub 6}S{sub 8{minus}z}:CoCP) determined by x-ray diffraction analysis. The nonstoichiometric range of CoCP was very narrow and the only CoCP with y = 1.6,8 {minus} z = 7.7 could be prepared as a single phase. The CoCP was evaluated as a cathode for lithium secondary batteries. 1M CiClO{sub 4} in PC was used as an electrolyte. The discharge properties and discharge-charge cycling properties were measured galvanostatically under constant current densities from 0.1 to 2.0 mA/cm{sup 2}. The cell exhibited good discharge performance; for example when the cell wasmore » discharged under a cd = 0.1 mA/cm{sup 2}, 4.8 Li/Co{sub 1.6}Mo{sub 6}S{sub 7.7} were incorporated before the cell voltage fell down to 1.0 V (energy density: 277 Wh/kg). Also a rechargeability of more than 200 cycles was observed at cd = 0.5 mA/cm{sup 2}. The curve of OCV with varying Li content in the CoCP was very flat and near 2.1 V. The x-ray analysis of lithium incorporated cobalt Chevrel phase, Li{sub x}CoCP, was two sets of hexagonal lattice parameters showing the existence of two types of Chevrel phases (having different lattice parameters) coexisting in a wide range of 0 {lt} x {lt} 4.5.« less

Frey's procedure for chronic pancreatitis improves the nutritional status of these patients.

PubMed

Sato, Hideaki; Ishida, Masaharu; Motoi, Fuyuhiko; Sakata, Naoaki; Aoki, Takeshi; Kudoh, Katsuyoshi; Ohtsuka, Hideo; Mizuma, Masamichi; Morikawa, Takanori; Hayashi, Hiroki; Nakagawa, Kei; Naitoh, Takeshi; Egawa, Shinich; Unno, Michiaki

2018-01-01

The aim of surgical intervention for chronic pancreatitis (CP) is to relieve symptoms and improve quality of life. However, the precise effect of surgery on the nutritional status of CP patients, which is often impaired by exocrine and endocrine pancreatic dysfunction, has not been elucidated. We conducted this study to evaluate whether Frey's procedure improves the nutritional status of CP patients. The nutritional status of 35 patients who underwent Frey's procedure for CP at our institute between April 2005 and December 2014, was assessed by the controlling nutritional status (CONUT) scoring before and 1 year after the surgery, and compared with that of seven CP patients who underwent pancreatoduodenectomy. The occurrence of postoperative hepatic steatosis was also monitored. The nutritional status improved after Frey's procedure, but not after pancreatoduodenectomy. The median postoperative CONUT score after Frey's procedure was significantly lower than the preoperative score (1.0 ± 0.5 vs. 4.0 ± 2.5; p < 0.001). Frey's procedure is superior to pancreatoduodenectomy for improving the nutritional status of CP patients.

Strategies for the Construction of Supramolecular Dimers versus Homoleptic 1D Coordination Polymers Starting from the Diphosphorus [Cp2Mo2(CO)4(η2‐P2)] Complex and Silver(I) Salts

PubMed Central

Elsayed Moussa, Mehdi; Fleischmann, Martin; Peresypkina, Eugenia V.; Dütsch, Luis; Seidl, Michael; Balázs, Gabor

2017-01-01

The reactions of the tetrahedral diphosphorus [Cp2Mo2(CO)4(η2‐P2)] (1; Cp = C5H5) complex with Ag[Al{OC(CF3)3}4] (AgTEF) (A) and Ag[FAl{OC(C6F5)(C6F10)}3] (AgFAl) (B) were studied. The first reaction led to the formation of the [Ag2(η2‐1)2(η1:η1‐1)2][TEF]2 (2) dimer and the [Ag2(η1:η1‐1)3]n[TEF]2n (3) coordination polymer, whereas the second reaction afforded the [Ag2(η1:η1‐1)2(η1‐CH2Cl2)2(η2‐C7H8)2][FAl]2 (4) or the [Ag2(η2‐1)2(η1:η1‐1)2][FAl]2 (5) dimer and the [Ag2(η1:η1‐1)4]n[FAl]2n (6) coordination polymer. In each case, the products obtained depended on the ratio of the reactants and/or the synthetic procedure. PMID:28943780

The radiometal makes a difference. Synthesis and preliminary characterisation of DOTA-minigastrin analogue complexes with Ga, Lu and Y.

PubMed

Maurin, Michał; Garnuszek, Piotr; Baran, Piotr; Pawlak, Dariusz; Mikołajczak, Renata

2015-01-01

The minigastrin analogue - CP04: DOTA-(DGlu)6-Ala-Tyr-Gly-Trp-Met-Asp-Phe-NH2 has been developed for CCK2R targeting. This analogue can be radiolabelled with 111In or 68Ga for imaging, or with 90Y and 177Lu for therapy. However, affinity of the chelator-peptide conjugates to the cell membrane receptors may vary depending on the metal incorporated into the complex. So far, there are no such studies for the ligands of gastrin/cholecystokinin receptor CCK2R. It is supposed that the reason for the differentiation of receptor affinity to the respective receptors is in the changes of structure of chelating system and their influence on the bioactive conformations of the metal conjugated peptides. Herein, we report on the radiolabeling of CP04 with 90Y, 177Lu and 68Ga and synthesis of cold CP04 complexes with respective stable metals for further structural and physico-chemical and biological studies. From 200 to 600 MBq of 90Y, 177Lu or 68Ga were used for radiolabelling of 20 μg of CP04 dissolved in ascorbic acid solution (50 mg/mL, pH 4.5). Non-radioactive complexes with Lu and Ga were synthesized in milligram amounts starting from 0.5 mg up to 5 mg of CP04 dissolved in ascorbic acid solution (50 mg/mL, pH 4.5) when using 2-molar excess of the metal ions. Complex formation needed 5 min in microwave oven or 12 min in thermo-block at 95°C. RP-HPLC isocratic method (Kinetex 150/4.6 mm; 25% AcN/0.1% TFA, 1 mL/min) with UV/Vis and radiometric detection was developed for investigation of the radiolabelled and "cold" complexes. For LC-MS investigations, HPLC method was modified replacing TFA by formic acid. Yields of CP04 radiolabelling were greater than 90% for all three radionuclides. The HPLC method enabled identification of these radio-complexes based on comparison to their non-radioactive equivalents. In all cases, chromatograms revealed peaks that could be attributed to the metal-CP04 complexes and to impurities (including methionine oxidation). LC-MS analysis of Ga and Lu complexes revealed conformity of the observed molecular ions to the predicted formulas (m/z 2116 and 2220 Da for Ga and Lu, respectively). Different chromatographic behaviour observed for Ga-CP04 complex comparing to Lu- and Y- labelled peptide (relative retention to CP04: 1.08, 0.86 and 0.85, respectively) suggest different coordination of the metal ions. Therefore, further studies are planned using the non-radioactive complexes in order to assess their structural conformations.

Measurements of branching fractions, polarizations, and direct CP-violation asymmetries in B+→ρ0K*+ and B+→f0(980)K*+ decays

NASA Astrophysics Data System (ADS)

Del Amo Sanchez, P.; Lees, J. P.; Poireau, V.; Prencipe, E.; Tisserand, V.; Garra Tico, J.; Grauges, E.; Martinelli, M.; Milanes, D. A.; Palano, A.; Pappagallo, M.; Eigen, G.; Stugu, B.; Sun, L.; Brown, D. N.; Kerth, L. T.; Kolomensky, Yu. G.; Lynch, G.; Osipenkov, I. L.; Koch, H.; Schroeder, T.; Asgeirsson, D. J.; Hearty, C.; Mattison, T. S.; McKenna, J. A.; Khan, A.; Blinov, V. E.; Buzykaev, A. R.; Druzhinin, V. P.; Golubev, V. B.; Kravchenko, E. A.; Onuchin, A. P.; Serednyakov, S. I.; Skovpen, Yu. I.; Solodov, E. P.; Todyshev, K. Yu.; Yushkov, A. N.; Bondioli, M.; Curry, S.; Kirkby, D.; Lankford, A. J.; Mandelkern, M.; Martin, E. C.; Stoker, D. P.; Atmacan, H.; Gary, J. W.; Liu, F.; Long, O.; Vitug, G. M.; Campagnari, C.; Hong, T. M.; Kovalskyi, D.; Richman, J. D.; West, C.; Eisner, A. M.; Heusch, C. A.; Kroseberg, J.; Lockman, W. S.; Martinez, A. J.; Schalk, T.; Schumm, B. A.; Seiden, A.; Winstrom, L. O.; Cheng, C. H.; Doll, D. A.; Echenard, B.; Hitlin, D. G.; Ongmongkolkul, P.; Porter, F. C.; Rakitin, A. Y.; Andreassen, R.; Dubrovin, M. S.; Mancinelli, G.; Meadows, B. T.; Sokoloff, M. D.; Bloom, P. C.; Ford, W. T.; Gaz, A.; Nagel, M.; Nauenberg, U.; Smith, J. G.; Wagner, S. R.; Ayad, R.; Toki, W. H.; Jasper, H.; Karbach, T. M.; Petzold, A.; Spaan, B.; Kobel, M. J.; Schubert, K. R.; Schwierz, R.; Bernard, D.; Verderi, M.; Clark, P. J.; Playfer, S.; Watson, J. E.; Andreotti, M.; Bettoni, D.; Bozzi, C.; Calabrese, R.; Cecchi, A.; Cibinetto, G.; Fioravanti, E.; Franchini, P.; Garzia, I.; Luppi, E.; Munerato, M.; Negrini, M.; Petrella, A.; Piemontese, L.; Baldini-Ferroli, R.; Calcaterra, A.; de Sangro, R.; Finocchiaro, G.; Nicolaci, M.; Pacetti, S.; Patteri, P.; Peruzzi, I. M.; Piccolo, M.; Rama, M.; Zallo, A.; Contri, R.; Guido, E.; Lo Vetere, M.; Monge, M. R.; Passaggio, S.; Patrignani, C.; Robutti, E.; Tosi, S.; Bhuyan, B.; Prasad, V.; Lee, C. L.; Morii, M.; Edwards, A. J.; Adametz, A.; Marks, J.; Uwer, U.; Bernlochner, F. U.; Ebert, M.; Lacker, H. M.; Lueck, T.; Volk, A.; Dauncey, P. D.; Tibbetts, M.; Behera, P. K.; Mallik, U.; Chen, C.; Cochran, J.; Crawley, H. B.; Dong, L.; Meyer, W. T.; Prell, S.; Rosenberg, E. I.; Rubin, A. E.; Gritsan, A. V.; Guo, Z. J.; Arnaud, N.; Davier, M.; Derkach, D.; Firmino da Costa, J.; Grosdidier, G.; Le Diberder, F.; Lutz, A. M.; Malaescu, B.; Perez, A.; Roudeau, P.; Schune, M. H.; Serrano, J.; Sordini, V.; Stocchi, A.; Wang, L.; Wormser, G.; Lange, D. J.; Wright, D. M.; Bingham, I.; Chavez, C. A.; Coleman, J. P.; Fry, J. R.; Gabathuler, E.; Gamet, R.; Hutchcroft, D. E.; Payne, D. J.; Touramanis, C.; Bevan, A. J.; di Lodovico, F.; Sacco, R.; Sigamani, M.; Cowan, G.; Paramesvaran, S.; Wren, A. C.; Brown, D. N.; Davis, C. L.; Denig, A. G.; Fritsch, M.; Gradl, W.; Hafner, A.; Alwyn, K. E.; Bailey, D.; Barlow, R. J.; Jackson, G.; Lafferty, G. D.; Anderson, J.; Cenci, R.; Jawahery, A.; Roberts, D. A.; Simi, G.; Tuggle, J. M.; Dallapiccola, C.; Salvati, E.; Cowan, R.; Dujmic, D.; Sciolla, G.; Zhao, M.; Lindemann, D.; Patel, P. M.; Robertson, S. H.; Schram, M.; Biassoni, P.; Lazzaro, A.; Lombardo, V.; Palombo, F.; Stracka, S.; Cremaldi, L.; Godang, R.; Kroeger, R.; Sonnek, P.; Summers, D. J.; Nguyen, X.; Simard, M.; Taras, P.; de Nardo, G.; Monorchio, D.; Onorato, G.; Sciacca, C.; Raven, G.; Snoek, H. L.; Jessop, C. P.; Knoepfel, K. J.; Losecco, J. M.; Wang, W. F.; Corwin, L. A.; Honscheid, K.; Kass, R.; Morris, J. P.; Blount, N. L.; Brau, J.; Frey, R.; Igonkina, O.; Kolb, J. A.; Rahmat, R.; Sinev, N. B.; Strom, D.; Strube, J.; Torrence, E.; Castelli, G.; Feltresi, E.; Gagliardi, N.; Margoni, M.; Morandin, M.; Posocco, M.; Rotondo, M.; Simonetto, F.; Stroili, R.; Ben-Haim, E.; Bonneaud, G. R.; Briand, H.; Calderini, G.; Chauveau, J.; Hamon, O.; Leruste, Ph.; Marchiori, G.; Ocariz, J.; Prendki, J.; Sitt, S.; Biasini, M.; Manoni, E.; Rossi, A.; Angelini, C.; Batignani, G.; Bettarini, S.; Carpinelli, M.; Casarosa, G.; Cervelli, A.; Forti, F.; Giorgi, M. A.; Lusiani, A.; Neri, N.; Paoloni, E.; Rizzo, G.; Walsh, J. J.; Lopes Pegna, D.; Lu, C.; Olsen, J.; Smith, A. J. S.; Telnov, A. V.; Anulli, F.; Baracchini, E.; Cavoto, G.; Faccini, R.; Ferrarotto, F.; Ferroni, F.; Gaspero, M.; Li Gioi, L.; Mazzoni, M. A.; Piredda, G.; Renga, F.; Hartmann, T.; Leddig, T.; Schröder, H.; Waldi, R.; Adye, T.; Franek, B.; Olaiya, E. O.; Wilson, F. F.; Emery, S.; Hamel de Monchenault, G.; Vasseur, G.; Yèche, Ch.; Zito, M.; Allen, M. T.; Aston, D.; Bard, D. J.; Bartoldus, R.; Benitez, J. F.; Cartaro, C.; Convery, M. R.; Dorfan, J.; Dubois-Felsmann, G. P.; Dunwoodie, W.; Field, R. C.; Franco Sevilla, M.; Fulsom, B. G.; Gabareen, A. M.; Graham, M. T.; Grenier, P.; Hast, C.; Innes, W. R.; Kelsey, M. H.; Kim, H.; Kim, P.; Kocian, M. L.; Leith, D. W. G. S.; Li, S.; Lindquist, B.; Luitz, S.; Luth, V.; Lynch, H. L.; Macfarlane, D. B.; Marsiske, H.; Muller, D. R.; Neal, H.; Nelson, S.; O'Grady, C. P.; Ofte, I.; Perl, M.; Pulliam, T.; Ratcliff, B. N.; Roodman, A.; Salnikov, A. A.; Santoro, V.; Schindler, R. H.; Schwiening, J.; Snyder, A.; Su, D.; Sullivan, M. K.; Sun, S.; Suzuki, K.; Thompson, J. M.; Va'Vra, J.; Wagner, A. P.; Weaver, M.; Wisniewski, W. J.; Wittgen, M.; Wright, D. H.; Wulsin, H. W.; Yarritu, A. K.; Young, C. C.; Ziegler, V.; Chen, X. R.; Park, W.; Purohit, M. V.; White, R. M.; Wilson, J. R.; Randle-Conde, A.; Sekula, S. J.; Bellis, M.; Burchat, P. R.; Miyashita, T. S.; Ahmed, S.; Alam, M. S.; Ernst, J. A.; Pan, B.; Saeed, M. A.; Zain, S. B.; Guttman, N.; Soffer, A.; Lund, P.; Spanier, S. M.; Eckmann, R.; Ritchie, J. L.; Ruland, A. M.; Schilling, C. J.; Schwitters, R. F.; Wray, B. C.; Izen, J. M.; Lou, X. C.; Bianchi, F.; Gamba, D.; Pelliccioni, M.; Bomben, M.; Lanceri, L.; Vitale, L.; Lopez-March, N.; Martinez-Vidal, F.; Oyanguren, A.; Albert, J.; Banerjee, Sw.; Choi, H. H. F.; Hamano, K.; King, G. J.; Kowalewski, R.; Lewczuk, M. J.; Lindsay, C.; Nugent, I. M.; Roney, J. M.; Sobie, R. J.; Gershon, T. J.; Harrison, P. F.; Latham, T. E.; Puccio, E. M. T.; Band, H. R.; Dasu, S.; Flood, K. T.; Pan, Y.; Prepost, R.; Vuosalo, C. O.; Wu, S. L.

2011-03-01

We present measurements of the branching fractions, longitudinal polarization, and direct CP-violation asymmetries for the decays B+→ρ0K*+ and B+→f0(980)K*+ with a sample of (467±5)×106BB¯ pairs collected with the BABAR detector at the PEP-II asymmetric-energy e+e- collider at the SLAC National Accelerator Laboratory. We observe B+→ρ0K*+ with a significance of 5.3σ and measure the branching fraction B(B+→ρ0K*+)=(4.6±1.0±0.4)×10-6, the longitudinal polarization fL=0.78±0.12±0.03, and the CP-violation asymmetry ACP=0.31±0.13±0.03. We observe B+→f0(980)K*+ and measure the branching fraction B(B+→f0(980)K*+)×B(f0(980)→π+π-)=(4.2±0.6±0.3)×10-6 and the CP-violation asymmetry ACP=-0.15±0.12±0.03. The first uncertainty quoted is statistical and the second is systematic.

Antioxidant activity and oxidative stress protection of duck proteins hydrolysates in SK-N-SH cells.

PubMed

Guo, Yuxing; Pan, Daodong; Wu, Zhen; Zhao, Chuanchuan; Cao, Jinxuan

2013-02-26

Studies have found that natural antioxidants, which are free-radical scavengers, can reduce the risk of diseases caused by free radicals. This work investigated the antioxidant properties of duck proteins hydrolysates. The free-radical scavenging function of CP-1 (M(r) > 10 kDa), CP-2 (5 kDa < M(r) < 10 kDa) and CP-3 (M(r) < 5 kDa), obtained through ultrafiltration and gel filtration were evaluated. The results showed that the lower molecular weight fraction exhibited a stronger free-radical scavenging ability. The highest free-radical scavenging activity was detected in the fraction of p4 purified from CP-3 using Sephadex G-15 column chromatography. The 50% inhibitory value (IC(50)) of p4 for scavenging radicals of superoxide, hydroxyl and 1,1-diphenyl-2-pycrylhydrazyl (DPPH) were, respectively, 0.97 mg mL(-1), 0.84 mg mL(-1) and 1.84 mg mL(-1). Furthermore, the p4 fraction at a concentration of 10 μg mL(-1) increased cell viability from 84.8% to 94% under antioxidative stress in neuroblastoma SK-N-SH cells.

Mechanical Properties and Wear Characteristics Al-ZrO2-SiCp and Graphite Hybrid Metal Matrix Composites

NASA Astrophysics Data System (ADS)

Nayak, S. K.; Mahanta, T.; Sahoo, J. K.; Mishra, A.

2018-03-01

Development of Aluminum Metal Matrix Co mposites (AMMCs) has been one of the major requirements in engineering applicat ions due to their excellent mechanical properties, light weight and high strength. In the present investigation, Stir casting technique has been used for fabrication of co mposites, taking Alu miniu m as parent metal, Silicon Carbide (SiCp) of 7 vol. % of 220 mesh size and 1.75 vol. % of graphite as reinforcements. The Zirconia content was varied as 2.75, 4.5 and 6 vol. % to fabricate three d ifferent types of hybrid composites. The tensile strength and hardness were measured in UTM and Vickers hardness tester respectively and the wear characteristics were studied in a pin on disc friction monitor under dry sliding condition against steel counter face. The tensile strength was found to be 90 MPa, 120 MPa, 130 MPa and hardness 80.25 VHN, 103.22 VHN, 103.77 VHN for 2.75, 4.5 and 6vol. % of Zirconia respectively. Fro m the above investigation, it is recommended that composition with Al, 7 %-SiCp, 1.75 % -Gr and 6 vol %-ZrO2 showed better mechanical p roperties i.e . h igh tensile strength (130MPa) and reasonably good hardness (103.77 VHN) . The co mposite with Al, 7 % - SiCp, 1.75 % -Gr and 6 %-ZrO2 is good for short run frictional applicat ion and the composite with Al, 7 %- SiCp, 1.75 % -Gr and 4.5 %- ZrO2 may be used for long run frictional applicat ions after testing.

The in vivo pharmacological profile of a 5-HT1 receptor agonist, CP-122,288, a selective inhibitor of neurogenic inflammation.

PubMed

Gupta, P; Brown, D; Butler, P; Ellis, P; Grayson, K L; Land, G C; Macor, J E; Robson, S F; Wythes, M J; Shepperson, N B

1995-11-01

1. The aim of the present study was to investigate the in vivo pharmacological profile of CP-122,288, an indole-derivative with a conformationally restricted N-methylpyrrolidinyl basic side chain in the C-3 position. This C-3 substituent structurally differentiates CP-122,288 from the 5-HT1D receptor agonist sumatriptan, which possesses an N,N-dimethylaminoethyl group. [Formula: see text] 2. When administered prior to electrical stimulation of the trigeminal ganglion, CP-122,288 (0.3-300 ng kg-1, i.v.) produced a dose-related inhibition of plasma protein extravasation in rat dura mater (minimum effective dose, MED, 3 ng kg-1 i.v., P < 0.05; maximal inhibition of plasma extravasation at 30 ng kg-1 i.v., P < 0.01). Sumatriptan produced a similar inhibition of plasma leakage in the dura, but at much higher dose levels (MED, 100 micrograms kg-1 i.v., P < 0.05). Thus, CP-122,288 is of the order of 10(4) fold more potent than sumatriptan. 3. At all doses tested, CP-122,288 did not inhibit plasma protein extravasation measured in extracranial tissues such as the lower lip, eyelid, and conjunctiva. 4. In a separate series of studies in the anaesthetized rat, CP-122,288 (0.003-3 micrograms kg-1 i.v.) produced no change in either heart rate or mean arterial blood pressure, thus demonstrating that doses of CP-122,288 which inhibit plasma protein leakage in rat dura, are devoid of hemodynamic effects. 5. Following a 5 min period of electrical stimulation of the trigeminal ganglion, a 20 min period of sustained neurogenically-driven plasma extravasation, occurring in the absence of electrical stimulation, was initiated. By administration of the compound 5 min after completing the phase of electrical stimulation, this protocol permitted the evaluation of the activity of CP-122,288 on an ongoing and established inflammatory event. CP-122,288 (30 and 300 ng kg-1, i.v., P < 0.01 and P < 0.05, respectively) produced a complete inhibition of plasma protein leakage which was consistent with its effects when administered prior to trigeminal ganglion stimulation. 6. In the anaesthetized dog, CP-122,288 and sumatriptan, at 1-300 micrograms kg-1, i.v., produced a dose-dependent reduction in carotid arterial blood flow and coronary arterial diameter. These data demonstrate that sumatriptan inhibits neurogenic inflammation in the rat (MED, 100 micrograms kg-1, i.v.), and produces vasoconstriction in the dog, over a similar dose-range. Interestingly, doses of CP-122,288 that inhibit neurogenic inflammation in rat dura mater (0.3-300 ng kg-1) were demonstrated to be devoid of vasoconstrictor activity in either the carotid or coronary vascular beds of dog. 7. These data demonstrate that in the rat, CP-122,288 is a highly potent and selective inhibitor of neurogenic inflammation in intracranial tissues, at doses which are devoid of vasoconstrictor activity in dog. Potentially, CP-122,288 may be of use for the acute treatment of migraine, without the risk of cardiovascular side-effects.

Synthesis of ruthenium(II) complexes containing hydroxymethylphosphines and their catalytic activities for hydrogenation of supercritical carbon dioxide.

PubMed

Kayaki, Yoshihito; Shimokawatoko, Yoshiki; Ikariya, Takao

2007-07-09

Ligand substitution of RuCl2[P(C6H5)3]3 and Cp*RuCl(isoprene) (Cp*=1,2,3,4,5-pentamethylcyclopentadienyl) complexes with hydroxymethylphosphines was investigated to develop new catalyst systems for CO2 hydrogenation. A reaction of P(C6H5)2CH2OH with RuCl2[P(C6H5)3]3 in CH2Cl2 gave Ru(H)Cl(CO)[P(C6H5)2CH2OH]3 (1), which was characterized by NMR spectroscopy and X-ray crystallographic analysis. An isotope labeling experiment using P(C6H5)213CH2OH indicated that the carbonyl moiety in complex 1 originated from formaldehyde formed by degradation of the hydroxymethylphosphine. Elimination of formaldehyde from PCy2CH2OH (Cy=cyclohexyl) was also promoted by treatment of RuCl2[P(C6H5)3]3 in ethanol to give RuCl2(PHCy2)4 under mild conditions. On the other hand, the substitution reaction using Cp*RuCl(isoprene) with the hydroxymethylphosphine ligands proceeded smoothly with formation of Cp*RuCl(L)2 [2a-2c; L=P(C6H5)2CH2OH, PCy(CH2OH)2, and P(CH2OH)3] in good yields. The isolable hydroxymethylphosphine complexes 1 and 2 efficiently catalyzed the hydrogenative amidation of supercritical carbon dioxide (scCO2) to N,N-dimethylformamide (DMF).

Patterns of tropical Pacific convection anomalies and associated extratropical wave trains in AMIP5

NASA Astrophysics Data System (ADS)

Ding, Shuoyi; Chen, Wen; Graf, Hans-F.; Guo, Yuanyuan

2018-05-01

In this paper, the performance of 18 Coupled Model Intercomparison Project Phase 5 (CMIP5) models forced by observational SSTs in simulating the tropical Pacific convective variation and the atmospheric responses in the extratropics are assessed. The multi-model ensemble mean results of 18 CMIP5 models show that five major patterns of tropical Pacific convection anomaly in winter can indeed be well reproduced, however, the simulation of the corresponding extratropical responses for each pattern exists some deficiency except for the La Niña pattern compared with observations. We defined an optimized subset of well performing models (ACCESS1.0, CanAM4, CCSM4, CMCC-CM, HadGEM2-A, MPI-ESM-MR) in tropical Pacific deep convection according to the ranking of model skill score. These models exhibit approximately identical convection anomaly patterns in both amplitude and spatial structure to the observation, which potentially might improve the representation of extratropical teleconnections with the tropical Pacific, especially for the CP El Niño (CPEN), EP El Niño (EPEN) and western CP (W-CP) patterns. Both evident atmospheric anomalies of CPEN and EPEN patterns over the NA/E sector and the northeastward propagating wave trains of W-CP pattern can be quite well simulated in the high-skilled models.

Deep brain stimulation for the treatment of childhood dystonic cerebral palsy.

PubMed

Keen, Joseph R; Przekop, Allison; Olaya, Joffre E; Zouros, Alexander; Hsu, Frank P K

2014-12-01

Deep brain stimulation (DBS) for dystonic cerebral palsy (CP) has rarely been reported, and its efficacy, though modest when compared with that for primary dystonia, remains unclear, especially in the pediatric population. The authors present a small series of children with dystonic CP who underwent bilateral pallidal DBS, to evaluate the treatment's efficacy and safety in the pediatric dystonic CP population. The authors conducted a retrospective review of patients (under the age of 18 years) with dystonic CP who had undergone DBS of the bilateral globus pallidus internus between 2010 and 2012. Two of the authors independently assessed outcomes using the Barry-Albright Dystonia Scale (BADS) and the Burke-Fahn-Marsden Dystonia Rating Scale-movement (BFMDRS-M). Five children were diagnosed with dystonic CP due to insults occurring before the age of 1 year. Mean age at surgery was 11 years (range 8-17 years), and the mean follow-up was 26.6 months (range 2-42 months). The mean target position was 20.6 mm lateral to the midcommissural point. The mean preoperative and postoperative BADS scores were 23.8 ± 4.9 (range 18.5-29.0) and 20.0 ± 5.5 (range 14.5-28.0), respectively, with a mean overall percent improvement of 16.0% (p = 0.14). The mean preoperative and postoperative BFMDRS-M scores were 73.3 ± 26.6 (range 38.5-102.0) and 52.4 ± 21.5 (range 34.0-80.0), respectively, with a mean overall percent improvement of 28.5% (p = 0.10). Those stimulated at least 23 months (4 patients) improved 18.3% (p = 0.14) on the BADS and 30.5% (p = 0.07) on the BFMDRS-M. The percentage improvement per body region yielded conflicting results between rating scales; however, BFMDRS-M scores for speech showed some of the greatest improvements. Two patients required hardware removal (1 complete system, 1 unilateral electrode) within 4 months after implantation because of infections that resolved with antibiotics. All postoperative dystonia rating scale scores improved with pallidal stimulation, and the greatest improvements occurred in those stimulated the longest. The results were modest but comparable to findings in other similar series. Deep brain stimulation remains a viable treatment option for childhood dystonic CP, although young children may have an increased risk of infection. Of particular note, improvements in the BFMDRS-M subscores for speech were comparable to those for other muscle groups, a finding not previously reported.

Theoretical Prediction on [5]Radialene Sandwich Complexes (CpM)2(C10H10) (Cp = η5-C5H5; M = Fe, Co, Ni): Geometry, Spin States, and Bonding.

PubMed

Liu, Nan-Nan; Xue, Ying-Ying; Ding, Yi-Hong

2017-02-09

[5]Radialene, the missing link for synthesis of radialene family, has been finally obtained via the preparation and decomplexation of the [5]radialene-bis-Fe(CO) 3 complex. The stability of [5]radialene complex benefits from the coordination with Fe(CO) 3 by losing free 1,3-butadiene structures to avoid polymerization. In light of the similar coordination ability of half-sandwiches CpM(Cp = η 5 -C 5 H 5 ; M = Fe, Co, Ni), there is a great possibility that the sandwiched complexes of [5]radialene with CpM are available. Herein, we present the first theoretical prediction on the geometry, spin states and bonding of (CpM)(C 10 H 10 ) and (CpM) 2 (C 10 H 10 ). For M = Fe, Co, Ni, the ground states of (CpM)(C 10 H 10 ) and (CpM) 2 (C 10 H 10 ) are doublet and triplet, singlet and singlet, and doublet and triplet states, where each Fe, Co, and Ni adopts 17, 18, and 19 electron-configuration, respectively. In particular, (CpFe) 2 (C 10 H 10 ) and (CpNi) 2 (C 10 H 10 ) have considerable open-shell singlet features. Generally the trans isomers of (CpM) 2 (C 10 H 10 ) with two CpM fragments on the opposite sides of the [5]radialene plane are apparently more stable than the cis ones with CpM fragments on the same side. However, for the singlet and triplet isomers of (CpNi) 2 (C 10 H 10 ) (both cis and trans isomers), the energy differences are relatively small, indicating that these isomers all have the opportunity to exist. Besides, the easy Diels-Alder (DA) dimerization between the [3]dendralene-like fragments of (CpM)(C 10 H 10 ) suggests the great difficulty in isolating the (CpM)(C 10 H 10 ) monomer.

Bioinspired Design and Computational Prediction of Iron Complexes with Pendant Amines for the Production of Methanol from CO2 and H2.

PubMed

Chen, Xiangyang; Yang, Xinzheng

2016-03-17

Inspired by the active site structure of [FeFe]-hydrogenase, we built a series of iron dicarbonyl diphosphine complexes with pendant amines and predicted their potentials to catalyze the hydrogenation of CO2 to methanol using density functional theory. Among the proposed iron complexes, [(P(tBu)2N(tBu)2H)FeH(CO)2(COOH)](+) (5COOH) is the most active one with a total free energy barrier of 23.7 kcal/mol. Such a low barrier indicates that 5COOH is a very promising low-cost catalyst for high-efficiency conversion of CO2 and H2 to methanol under mild conditions. For comparison, we also examined Bullock's Cp iron diphosphine complex with pendant amines, [(P(tBu)2N(tBu)2H)FeHCp(C5F4N)](+) (5Cp-C5F4N), as a catalyst for hydrogenation of CO2 to methanol and obtained a total free energy barrier of 27.6 kcal/mol, which indicates that 5Cp-C5F4N could also catalyze the conversion of CO2 and H2 to methanol but has a much lower efficiency than our newly designed iron complexes.

Two Discrete RuCp* (Cp*=Pentamethylcyclopentadienyl) Binding Modes of N-Confused Porphyrins: Peripheral π Complex and Sitting Atop Ruthenocenophane Complex by Skeletal Transformation.

PubMed

Yamamoto, Takaaki; Mitsuno, Koki; Mori, Shigeki; Itoyama, Shuhei; Shiota, Yoshihito; Yoshizawa, Kazunari; Ishida, Masatoshi; Furuta, Hiroyuki

2018-05-07

Complexation of a RuCp* cation with N-confused tetraarylporphyrins (NCPs) forms directly bound ruthenium(II) pentamethylcyclopentadienyl (Cp*) π-complex on a specific meso-aryl group (e.g., phenyl) neighboring peripheral imino nitrogen of NCPs in high yields. In contrast, in the case of NCPs bearing bulky meso-substituents (e.g., 3,5-di-tert-butylphenyl), new ruthenocenophane-like complex embedded on an N-confused calix[4]phyrin was formed through multiple C-H bond activation of methyl groups of Cp* ligand. The mechanistic insight into the formation of the ruthenocenophane was derived from DFT calculations. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Cp*Co(III) catalysts with proton-responsive ligands for carbon dioxide hydrogenation in aqueous media.

PubMed

Badiei, Yosra M; Wang, Wan-Hui; Hull, Jonathan F; Szalda, David J; Muckerman, James T; Himeda, Yuichiro; Fujita, Etsuko

2013-11-04

New water-soluble pentamethylcyclopentadienyl cobalt(III) complexes with proton-responsive 4,4'- and 6,6'-dihydroxy-2,2'-bipyridine (4DHBP and 6DHBP, respectively) ligands have been prepared and were characterized by X-ray crystallography, UV-vis and NMR spectroscopy, and mass spectrometry. These cobalt(III) complexes with proton-responsive ligands predominantly exist in their deprotonated [Cp*Co(DHBP-2H(+))(OH2)] forms with stronger electron-donating properties in neutral and basic solutions, and are active catalysts for CO2 hydrogenation in aqueous bicarbonate media at moderate temperature under a total 4-5 MPa (CO2:H2 1:1) pressure. The cobalt complexes containing 4DHBP ligands ([1-OH2](2+) and [1-Cl](+), where 1 = Cp*Co(4DHBP)) display better thermal stability and exhibit notable catalytic activity for CO2 hydrogenation to formate in contrast to the catalytically inactive nonsubstituted bpy analogues [3-OH2](2+) (3 = Cp*Co(bpy)). While the catalyst Cp*Ir(6DHBP)(OH2)(2+) in which the pendent oxyanion lowers the barrier for H2 heterolysis via proton transfer through a hydrogen-bonding network involving a water molecule is remarkably effective (ACS Catal. 2013, 3, 856-860), cobalt complexes containing 6DHBP ligands ([2-OH2](2+) and [2-Cl](+), 2 = Cp*Co(6DHBP)) exhibit lower TOF and TON for CO2 hydrogenation than those with 4DHBP. The low activity is attributed to thermal instability during the hydrogenation of CO2 as corroborated by DFT calculations.

Anti-inflammatory cytokines in gingival crevicular fluid in patients with periodontitis and rheumatoid arthritis: a preliminary report.

PubMed

Bozkurt, Fatma Yeşim; Yetkin Ay, Zuhal; Berker, Ezel; Tepe, Eser; Akkuş, Selami

2006-08-01

Cytokines which are produced by host cells play an important role in pathogenesis both rheumatoid arthritis (RA) and chronic periodontitis (CP). In this study, we aim to investigate the levels of Interleukin (IL)-4 and IL-10 in gingival crevicular fluid (GCF). Seventeen patients with CP, 17 patients with RA and 17 healthy controls (HC) were included. The RA group was divided into two groups according to gingival sulcus depths (RA-a: PD < or =3mm, (n=12), RA-b: PD>3mm, (n=5)). For each patient, clinical parameters were recorded. The GCF samples were evaluated by enzyme-linked immunosorbent assay (ELISA) for IL-4 and IL-10 levels. IL-4 levels in the RA-a, RA-b and CP subjects were significantly lower compared to the HC subjects (p<0.05). The mean level of IL-4 in RA-b group was significantly higher than that in CP group (p<0.05). IL-10 mean level in the HC group was higher than those in the other groups (p<0.05). In the RA-a group, higher IL-10 level was found compared to the CP patients (p<0.05). Within the limitations of this preliminary report, it can be concluded that the initiation and progression of periodontal inflammation may be due to a lack or inappropriate response of the anti-inflammatory cytokines in both CP and RA.

Bevacizumab plus chemotherapy for patients with advanced pulmonary adenocarcinoma harboring EGFR mutations.

PubMed

Chen, R-L; Chen, H-J; Jiang, B-Y; Zhang, X-C; Zhou, Q; Tu, H-Y; Zhong, W-Z; Wu, Y-L; Yang, J-J

2018-02-01

Epidermal growth factor receptor (EGFR) tyrosine kinase inhibitors (TKIs) and bevacizumab plus chemotherapy were effective for EGFR-mutant patients. However, the appropriated treatment orders remained controvertible. We investigated the efficacy of treatment orders between bevacizumab plus chemotherapy and EGFR-TKIs for EGFR-mutant patients with advanced pulmonary adenocarcinoma. This study involved 40 EGFR-mutant patients with advanced pulmonary adenocarcinoma who were treated with bevacizumab plus carboplatin and paclitaxel (Bev + CP) and EGFR-TKIs in different treatment orders or gemcitabine plus cisplatin (GP) in first-line setting. Seventeen patients were treated with Bev + CP and 10 cases with GP in first-line treatment. Thirteen patients received EGFR-TKIs after first-line Bev + CP regimen, while 13 patients were treated with first-line EGFR-TKIs. Progression-free survival (PFS), the response rate (ORR) and overall survival (OS) were evaluated. Median PFS of Bev + CP treatment was significantly longer in first-line than non-first-line settings (11.7 vs. 5.6 months, P = 0.003). Median OS was 37.8 months for EGFR-mutant patients with first-line Bev + CP followed by second-line EGFR-TKIs and 31.0 months for those with first-line EGFR-TKIs and non-first-line Bev + CP, respectively (P = 0.509). Median PFS was 11.7 (95% CI 10.6-12.8) months for Bev + CP group and 4.7 (95% CI 4.4-5.0) months for GP group with the hazard ratio of 0.17 (P = 0.001). ORR was 70.6 and 50.0% in the two groups, respectively (P = 0.415). However, there was no significant difference in median OS (33.7 vs 27.8 months, P = 0.293). First-line Bev + CP followed by EGFR-TKIs might possibly provide favorable prognosis for EGFR-mutant patients. Bev + CP regimen significantly prolonged PFS in first-line than non-first-line settings. These findings warrant further investigations.

Incidence and mortality of acute and chronic pancreatitis in the Netherlands: a nationwide record-linked cohort study for the years 1995-2005.

PubMed

Spanier, B W Marcel; Bruno, Marco J; Dijkgraaf, Marcel G W

2013-05-28

To analyze trends in incidence and mortality of acute pancreatitis (AP) and chronic pancreatitis (CP) in the Netherlands and for international standard populations. A nationwide cohort is identified through record linkage of hospital data for AP and CP, accumulated from three nationwide Dutch registries: the hospital discharge register, the population register, and the death certificate register. Sex- and age-group specific incidence rates of AP and CP are defined for the period 2000-2005 and mortality rates of AP and CP for the period 1995-2005. Additionally, incidence and mortality rates over time are reported for Dutch and international (European and World Health Organization) standard populations. Incidence of AP per 100000 persons per year increased between 2000 and 2005 from 13.2 (95%CI: 12.6-13.8) to 14.7 (95%CI: 14.1-15.3). Incidence of AP for males increased from 13.8 (95%CI: 12.9-14.7) to 15.2 (95%CI: 14.3-16.1), for females from 12.7 (95%CI: 11.9-13.5) to 14.2 (95%CI: 13.4-15.1). Irregular patterns over time emerged for CP. Overall mean incidence per 100000 persons per year was 1.77, for males 2.16, and for females 1.4. Mortality for AP fluctuated during 1995-2005 between 6.9 and 11.7 per million persons per year and was almost similar for males and females. Concerning CP, mortality for males fluctuated between 1.1 (95%CI: 0.6-2.3) and 4.0 (95%CI: 2.8-5.8), for females between 0.7 (95%CI: 0.3-1.6) and 2.0 (95%CI: 1.2-3.2). Incidence and mortality of AP and CP increased markedly with age. Standardized rates were lowest for World Health Organization standard population. Incidence of AP steadily increased while incidence of CP fluctuated. Mortality for both AP and CP remained fairly stable. Patient burden and health care costs probably will increase because of an ageing Dutch population.

Comparing Child-Pugh, MELD, and FIB-4 to Predict Clinical Outcomes in Hepatitis C Virus-Infected Persons: Results From ERCHIVES.

PubMed

Butt, Adeel A; Ren, Yanjie; Lo Re, Vincent; Taddei, Tamar H; Kaplan, David E

2017-07-01

Identifying hepatitis C virus (HCV)-positive persons at high risk of early complications can help prioritize treatment decisions. We conducted this study to compare Child-Turcotte-Pugh (CP), MELD, and FIB-4 scores for predicting clinical outcomes and to identify those at low risk of complications. Within electronically retrieved cohort of HCV-infected veterans, we identified HCV-positive persons and excluded those with human immunodeficiency virus (HIV), hepatitis B surface antigen (HBsAg), prevalent hepatic decompensation (HD), hepatocellular carcinoma (HCC), and those treated for HCV. We calculated incidence rates for HD, HCC, and all-cause mortality at 1, 3, and 5 years after HCV diagnosis. Using receiver operating characteristic (ROC) curves, we determined the optimal cut-off values for each score for these outcomes. Among 21 116 persons evaluated, 89.7% were CP Class-A, 79.9% had MELD<9, and 43.4% had FIB-4<1.45. AUROC for HD at 1, 3, and 5 years was higher for FIB-4 (0.84-0.86) compared with MELD (0.70-0.76) (P < .001). AUROC for HCC at 1, 3, and 5 years was 0.81-0.82 for FIB-4 but 0.61-0.68 for CP and MELD scores. (P < .001) AUROC for all-cause mortality at 3 and 5 years was 0.65-0.68. The optimal cut-off scores to identify persons at low risk of complications were as follows: CP <5; MELD <8; FIB-4 <3 for HD and HCC, and <2 for all-cause mortality, below which <1.5% developed HD and HCC and ≤2.5% died at 3 years. FIB-4 score is a better predictor of HD and HCC in HCV-positive persons. A score of <3 is associated with a low risk of HD and HCC 1 and 3 years after HCV diagnosis. © The Author 2017. Published by Oxford University Press for the Infectious Diseases Society of America. All rights reserved. For permissions, e-mail: journals.permissions@oup.com

Simultaneous identification and quantification of 4-cumylphenol, 2,4-bis-(dimethylbenzyl)phenol and bisphenol A in prawn Macrobrachium rosenbergii.

PubMed

Zuo, Yuegang; Zhu, Zhuo

2014-07-01

Bisphenol A (BPA), 4-cumylphenol (4-CP) and 2,4-bis-(dimethylbenzyl)phenol (2,4-DCP) are all high production volume chemicals and widely used in plastic and other consumer products. During the past two decades, BPA has attracted a great deal of scientific and public attention due to its presence in the environment and estrogenic property. Although 4-CP and 2,4-DCP are much more estrogenic and toxic than BPA, little information is available about their occurrence and fate in the environment. In this study, a rapid, selective, accurate and reliable analytical method was developed for the simultaneous determination of 4-CP, 2,4-DCP and BPA in prawn Macrobrachium rosenbergii. The method comprises an ultrasound-accelerated extraction followed by capillary gas chromatographic (GC) separation. The detection limits range from 1.50 to 36.4 ng kg(-1) for the three alkylphenols. The calibration curves are linear over the concentration range tested with the coefficients of determination, R(2), greater than 0.994. The developed method was successfully applied to the simultaneous determination of 4-CP, 2,4-DCP and BPA in prawn samples. The peak identification was confirmed using GC-MS. Bisphenol A, 2,4-bis-(dimethylbenzyl)phenol and 4-cumylphenol were found in prawn samples in the concentration ranges of 0.67-5.51, 0.36-1.61, and 0.00-1.96 ng g(-1) (wet weight), respectively. All relative standard deviations are less than 4.8%. At these environmentally relevant concentration levels, 4-CP, 2,4-DCP and BPA may affect the reproduction and development of aquatic organisms, including negative influence on crustaceans' larval survival, molting, metamorphosis and shell hardening. This is the first study reported on the occurrence of 4-CP, 2,4-DCP and BPA in prawn M. rosenbergii. Copyright © 2014 Elsevier Ltd. All rights reserved.

Dopamine and serotonin transporter genotypes moderate sensitivity to maternal expressed emotion: the case of conduct and emotional problems in attention deficit/hyperactivity disorder.

PubMed

Sonuga-Barke, Edmund J S; Oades, Robert D; Psychogiou, Lamprini; Chen, Wai; Franke, Barbara; Buitelaar, Jan; Banaschewski, Tobias; Ebstein, Richard P; Gil, Michael; Anney, Richard; Miranda, Ana; Roeyers, Herbert; Rothenberger, Aribert; Sergeant, Joseph; Steinhausen, Hans Christoph; Thompson, Margaret; Asherson, Philip; Faraone, Stephen V

2009-09-01

Mothers' positive emotions expressed about their children with attention deficit/hyperactivity disorder (ADHD) are associated with a reduced likelihood of comorbid conduct problems (CP). We examined whether this association with CP, and one with emotional problems (EMO), is moderated by variants within three genes, previously reported to be associated with ADHD and to moderate the impact of environmental risks on conduct and/or emotional problems; the dopamine transporter gene (SLC6A3/DAT1), the dopamine D4 receptor gene (DRD4) and the serotonin transporter gene (SLC6A4/5HTT). Seven hundred and twenty-eight males between the ages of 5 and 17 with a DSM-IV research diagnosis of combined type ADHD were included in these analyses. Parents and teachers rated children's conduct and emotional problems. Positive maternal expressed emotion (PMEE) was coded by independent observers on comments made during a clinical assessment with the mother based on current or recent medication-free periods. Sensitivity to the effects of PMEE on CP was moderated by variants of the DAT1 and 5HTT genes. Only children who did not carry the DAT1 10R/10R or the 5HTT l/l genotypes showed altered levels of CP when exposed to PMEE. The effect was most marked where the child with ADHD had both these genotypes. For EMO, sensitivity to PMEE was found only with those who carried the DAT1 9R/9R. There was no effect of DRD4 on CP or EMO. The gene-environment interactions observed suggested that genetic make-up can alter the degree of sensitivity an ADHD patients has to their family environment. Further research should focus on distinguishing general sensitivity genotypes from those conferring risk or protective qualities.

Synthesis of the water soluble ligands dmPTA and dmoPTA and the complex [RuClCp(HdmoPTA)(PPh(3))](OSO(2)CF(3)) (dmPTA = N,N'-Dimethyl-1,3,5-triaza-7-phosphaadamantane, dmoPTA = 3,7-Dimethyl-1,3,7-triaza-5-phosphabicyclo[3.3.1]nonane, HdmoPTA = 3,7-H-3,7-Dimethyl-1,3,7-triaza-5-phosphabicyclo[3.3.1]nonane).

PubMed

Mena-Cruz, Adrian; Lorenzo-Luis, Pablo; Romerosa, Antonio; Saoud, Mustapha; Serrano-Ruiz, Manuel

2007-07-23

The new water-soluble ligand dmPTA(OSO(2)CF(3))(2) (1) (dmPTA = N,N'-dimethyl-1,3,5-triaza-7-phosphaadamantane) has been synthesized by reaction of PTA with MeOSO(2)CF(3) in acetone (PTA = 1,3,5-triaza-7-phosphatricycle[3.3.1.1(3,7)]decane). The reaction of 1 with KOH gave rise to the new water-soluble ligand dmoPTA (3) (dmoPTA = 3,7-dimethyl-1,3,7-triaza-5-phosphabicyclo[3.3.1]nonane) by elimination of the -CH(2)- group located between both NCH(3) units. Compound dmPTA(BF(4))(2) (2) and complex [RuClCp(HdmoPTA)(PPh(3))](OSO(2)CF(3)) (4) have also been synthesized, while compounds HdmoPTA(BF(4)) (3a) and [RuClCp(dmPTA)(PPh(3))](OSO(2)CF(3)) (5) were characterized but not isolated. The new ligands and the complex have been fully characterized by NMR, IR, elemental analysis, and X-ray crystal structure determination (ligand 1 and complex 4). The synthetic processes for 3 and 4 were studied.

High-performance colossal permittivity materials of (Nb + Er) co-doped TiO2 for large capacitors and high-energy-density storage devices.

PubMed

Tse, Mei-Yan; Wei, Xianhua; Hao, Jianhua

2016-09-21

The search for colossal permittivity (CP) materials is imperative because of their potential for promising applications in the areas of device miniaturization and energy storage. High-performance CP materials require high dielectric permittivity, low dielectric loss and relatively weak dependence of frequency- and temperature. In this work, we first investigate the CP behavior of rutile TiO2 ceramics co-doped with niobium and erbium, i.e., (Er0.5Nb0.5)xTi1-xO2. Excellent dielectric properties were observed in the materials, including a CP of up to 10(4)-10(5) and a low dielectric loss (tan δ) down to 0.03, which are lower than that of the previously reported co-doped TiO2 CP materials when measured at 1 kHz. Stabilities of frequency and temperature were also accomplished via doping Er and Nb. Valence states of the elements in the material were analyzed using X-ray photoelectron spectroscopy. The Er induced secondary phases were observed using elemental mapping and energy-dispersive spectrometry. Consequently, this work may provide comprehensive guidance to develop high-performance CP materials for fully solid-state capacitor and energy storage applications.

Metallurgy and deformation of electron beam welded similar titanium alloys

NASA Astrophysics Data System (ADS)

Pasang, T.; Sabol, J. C.; Misiolek, W. Z.; Mitchell, R.; Short, A. B.; Littlefair, G.

2012-04-01

Butt welded joins were produced between commercially pure titanium and various titanium alloys using an electron beam welding technique. The materials used represent commercially pure grade, α-β alloy and β alloy. They were CP Ti, Ti-6Al-4V (Ti64) and Ti-5Al-5V-5Mo-3Cr (Ti5553), respectively. Grains were largest in the FZs of the different weldments, decreasing in size towards the heat affected zones (HAZs) and base metals. Hardness measurements taken across the traverse cross-sections of the weldments were constant from base metal-to-weld-to-base metal for CP Ti/CP Ti and Ti64/Ti64 welds, while the FZ of Ti5553/Ti5553 had a lower hardness compared with the base metal. During tensile testing the CP Ti/CP Ti weldments fractured at the base metal, whereas both the Ti64/Ti64 and Ti5553/Ti5553 broke at the weld zones. Fracture surface analysis suggested microvoid coalescence as the failure mechanism. The compositional analysis showed a relatively uniform distribution of solute elements from base metal-to-weld-to-base metal. CP Ti has always been known for its excellent weldability, Ti64 has good weldability and, preliminary results indicated that Ti5553 alloy is also weldable.

Synthesis, characterization and biological evaluation of a (67)Ga-labeled (η(6)-Tyr)Ru(η(5)-Cp) peptide complex with the HAV motif.

PubMed

Bihari, Zsolt; Vultos, Filipe; Fernandes, Célia; Gano, Lurdes; Santos, Isabel; Correia, João D G; Buglyó, Péter

2016-07-01

Heterobimetallic complexes with the evolutionary, well-preserved, histidyl-alanyl-valinyl (HAV) sequence for cadherin targeting, an organometallic Ru core with anticancer activity and a radioactive moiety for imaging may hold potential as theranostic agents for cancer. Visible-light irradiation of the HAVAY-NH2 pentapeptide in the presence of [(η(5)-Cp)Ru(η(6)-naphthalene)](+) resulted in the formation of a full sandwich type complex, (η(6)-Tyr-RuCp)-HAVAY-NH2 in aqueous solution, where the metal ion is connected to the Tyr (Y) unit of the peptide. Conjugation of this complex to 2,2'-(7-(1-carboxy-4-((4-isothiocyanatobenzyl)amino)-4-oxobutyl)-1,4,7-triazonane-1,4-diyl)diacetic acid (NODA-GA) and subsequent metalation of the resulting product with stable ((nat)Ga) and radioactive ((67)Ga) isotope yielded (nat)Ga/(67)Ga-NODA-GA-[(η(6)-Tyr-RuCp)-HAVAY-NH2]. The non-radioactive compounds were characterized by NMR spectroscopy and Mass Spectrometry. The cellular uptake and cytotoxicity of the radioactive and non-radioactive complexes, respectively, were evaluated in various human cancer cell lines characterized by different levels of N- or E-cadherins expression. Results from these studies indicate moderate cellular uptake of the radioactive complexes. However, the inhibition of the cell proliferation was not relevant. Copyright © 2016 Elsevier Inc. All rights reserved.

Antibodies to Staphylococcus aureus capsular polysaccharides 5 and 8 perform similarly in vitro but are functionally distinct in vivo.

PubMed

Liu, Bo; Park, Saeyoung; Thompson, Christopher D; Li, Xue; Lee, Jean C

2017-08-18

The capsular polysaccharide (CP) produced by Staphylococcus aureus is a virulence factor that allows the organism to evade uptake and killing by host neutrophils. Polyclonal antibodies to the serotype 5 (CP5) and type 8 (CP8) capsular polysaccharides are opsonic and protect mice against experimental bacteremia provoked by encapsulated staphylococci. Thus, passive immunotherapy using CP antibodies has been considered for the prevention or treatment of invasive antibiotic-resistant S. aureus infections. In this report, we generated monoclonal antibodies (mAbs) against S. aureus CP5 or CP8. Backbone specific mAbs reacted with native and O-deacetylated CPs, whereas O-acetyl specific mAbs reacted only with native CPs. Reference strains of S. aureus and a selection of clinical isolates reacted by colony immunoblot with the CP5 and CP8 mAbs in a serotype-specific manner. The mAbs mediated in vitro CP type-specific opsonophagocytic killing of S. aureus strains, and mice passively immunized with CP5 mAbs were protected against S. aureus bacteremia. Neither CP8-specific mAbs or polyclonal antibodies protected mice against bacteremia provoked by serotype 8 S. aureus clinical isolates, although these same antibodies did protect against a serotype 5 S. aureus strain genetically engineered to produce CP8. We detected soluble CP8 in culture supernatants of serotype 8 clinical isolates and in the plasma of infected animals. Serotype 5 S. aureus released significantly less soluble CP5 in vitro and in vivo. The release of soluble CP8 by S. aureus may contribute to the inability of CP8 vaccines or antibodies to protect against serotype 8 staphylococcal infections.

Biological Effect of Leaf Aqueous Extract of Caesalpinia pyramidalis in Goats Naturally Infected with Gastrointestinal Nematodes

PubMed Central

Borges-dos-Santos, Roberto Robson; López, Jorge A.; Santos, Luciano C.; Zacharias, Farouk; David, Jorge Maurício; David, Juceni Pereira; Lima, Fernanda Washington de Mendonça

2012-01-01

Forty-eight goats naturally infected with gastrointestinal nematodes were randomly divided into four groups (n = 12): negative control (G1) (untreated), positive control (G2) (treated with doramectin, 1 mL/50 Kg b.w.), and G3 and G4 treated with 2.5 and 5 mg/Kg b.w. of a leaf aqueous extract of Caesalpinia pyramidalis (CP). Fecal and blood samples were regularly collected for the evaluation of fecal egg count (FEC), hematological and immunological parameters to assess the anthelmintic activity. In treated animals with CP, there was noted a significant reduction of 54.6 and 71.2% in the mean FEC (P < 0.05). An increase in IgA levels was observed in G3 and G4 (P < 0.05), during the experimental period, suggesting that it was stimulated by the extract administration. In conclusion, the results showed that CP provoked a protective response in infected animals treated with them. This response could be partly explained by the CP chemical composition. PMID:22548117

Biodegradation and bioremediation potential of diazinon-degrading Serratia marcescens to remove other organophosphorus pesticides from soils.

PubMed

Cycoń, Mariusz; Żmijowska, Agnieszka; Wójcik, Marcin; Piotrowska-Seget, Zofia

2013-03-15

The ability of diazinon-degrading Serratia marcescens to remove organophosphorus pesticides (OPPs), i.e. chlorpyrifos (CP), fenitrothion (FT), and parathion (PT) was studied in a mineral salt medium (MSM) and in three soils of different characteristics. This strain was capable of using all insecticides at concentration of 50 mg/l as the only carbon source when grown in MSM, and 58.9%, 70.5%, and 82.5% of the initial dosage of CP, FT, and PT, respectively was degraded within 14 days. The biodegradation experiment showed that autochthonous microflora in all soils was characterized by a degradation potential of all tested OPPs; however, the initial lag phases for degradation of CP and FT, especially in sandy soil, were observed. During the 42-day experiment, 45.3%, 61.4% and 72.5% of the initial dose of CP, FT, and PT, respectively, was removed in sandy soil whereas the degradation of CP, FT, and PT in the same period, in sandy loam and silty soils reached 61.4%, 79.7% and 64.2%, and 68.9%, 81.0% and 63.6%, respectively. S. marcescens introduced into sterile soils showed a higher degradation potential (5-13%) for OPPs removal than those observed in non-sterile soil with naturally occurring attenuation. Inoculation of non-sterile soils with S. marcescens enhanced the disappearance rates of all insecticides, and DT50 for CP, FT, and PT was reduced by 20.7, 11.3 and 13.0 days, and 11.9, 7.0 and 8.1 days, and 9.7, 14.5 and 12.6 days in sandy, sandy loam, and silty soils, respectively, in comparison with non-sterile soils with only indigenous microflora. This ability of S. marcescens makes it a suitable strain for bioremediation of soils contaminated with OPPs. Copyright © 2013 Elsevier Ltd. All rights reserved.

Evidence for Isospin Violation and Measurement of CP Asymmetries in B→K^{*}(892)γ.

PubMed

Horiguchi, T; Ishikawa, A; Yamamoto, H; Adachi, I; Aihara, H; Al Said, S; Asner, D M; Aulchenko, V; Aushev, T; Ayad, R; Babu, V; Badhrees, I; Bakich, A M; Bansal, V; Behera, P; Bhardwaj, V; Bhuyan, B; Biswal, J; Bobrov, A; Bonvicini, G; Bozek, A; Bračko, M; Browder, T E; Červenkov, D; Chekelian, V; Chen, A; Cheon, B G; Chilikin, K; Cho, K; Choi, Y; Cinabro, D; Czank, T; Dash, N; Di Carlo, S; Doležal, Z; Drásal, Z; Dutta, D; Eidelman, S; Epifanov, D; Farhat, H; Fast, J E; Ferber, T; Fulsom, B G; Gaur, V; Gabyshev, N; Garmash, A; Gelb, M; Gillard, R; Goldenzweig, P; Golob, B; Guan, Y; Guido, E; Haba, J; Hara, T; Hayasaka, K; Hayashii, H; Hedges, M T; Higuchi, T; Hirose, S; Hou, W-S; Iijima, T; Inami, K; Inguglia, G; Itoh, R; Iwasaki, Y; Jacobs, W W; Jaegle, I; Jeon, H B; Jia, S; Jin, Y; Joffe, D; Joo, K K; Julius, T; Kang, K H; Kawasaki, T; Kim, D Y; Kim, J B; Kim, K T; Kim, M J; Kim, S H; Kim, Y J; Kinoshita, K; Kodyš, P; Korpar, S; Kotchetkov, D; Križan, P; Krokovny, P; Kuhr, T; Kulasiri, R; Kumar, R; Kumita, T; Kuzmin, A; Kwon, Y-J; Lange, J S; Li, C H; Li, L; Li Gioi, L; Libby, J; Liventsev, D; Lubej, M; Luo, T; Masuda, M; Matsuda, T; Matvienko, D; Merola, M; Miyabayashi, K; Miyata, H; Mizuk, R; Mohanty, G B; Mohanty, S; Moon, H K; Mori, T; Mussa, R; Nakano, E; Nakao, M; Nanut, T; Nath, K J; Natkaniec, Z; Nayak, M; Nisar, N K; Nishida, S; Ogawa, S; Okuno, S; Ono, H; Pakhlov, P; Pakhlova, G; Pal, B; Pardi, S; Park, C-S; Park, H; Paul, S; Pedlar, T K; Pestotnik, R; Piilonen, L E; Prasanth, K; Pulvermacher, C; Rauch, J; Rostomyan, A; Sakai, Y; Sandilya, S; Santelj, L; Savinov, V; Schneider, O; Schnell, G; Schwanda, C; Schwartz, A J; Seino, Y; Senyo, K; Seong, I S; Sevior, M E; Shebalin, V; Shen, C P; Shibata, T-A; Shiu, J-G; Simon, F; Sokolov, A; Solovieva, E; Starič, M; Strube, J F; Sumisawa, K; Sumiyoshi, T; Takizawa, M; Tamponi, U; Tanida, K; Tenchini, F; Trabelsi, K; Uchida, M; Uglov, T; Unno, Y; Uno, S; Urquijo, P; Ushiroda, Y; Usov, Y; Van Hulse, C; Varner, G; Vinokurova, A; Vorobyev, V; Vossen, A; Wang, C H; Wang, M-Z; Wang, P; Watanabe, Y; Watanuki, S; Weber, T; Widmann, E; Won, E; Yamashita, Y; Ye, H; Zhang, Z P; Zhilich, V; Zhukova, V; Zhulanov, V; Zupanc, A

2017-11-10

We report the first evidence for isospin violation in B→K^{*}γ and the first measurement of the difference of CP asymmetries between B^{+}→K^{*+}γ and B^{0}→K^{*0}γ. This analysis is based on the data sample containing 772×10^{6}BB[over ¯] pairs that was collected with the Belle detector at the KEKB energy-asymmetric e^{+}e^{-} collider. We find evidence for the isospin violation with a significance of 3.1σ, Δ_{0+}=[+6.2±1.5(stat)±0.6(syst)±1.2(f_{+-}/f_{00})]%, where the third uncertainty is due to the uncertainty on the fraction of B^{+}B^{-} to B^{0}B[over ¯]^{0} production in ϒ(4S) decays. The measured value is consistent with predictions of the standard model. The result for the difference of CP asymmetries is ΔA_{CP}=[+2.4±2.8(stat)±0.5(syst)]%, consistent with zero. The measured branching fractions and CP asymmetries for charged and neutral B meson decays are the most precise to date. We also calculate the ratio of branching fractions of B^{0}→K^{*0}γ to B_{s}^{0}→ϕγ.

Chorioamnionitis in the Development of Cerebral Palsy: A Meta-analysis and Systematic Review

PubMed Central

Ma, Lin; Luo, Kehuan; Bajaj, Monika; Chawla, Sanjay; Natarajan, Girija; Hagberg, Henrik; Tan, Sidhartha

2017-01-01

CONTEXT: Chorioamnionitis (CA) has often been linked etiologically to cerebral palsy (CP). OBJECTIVES: To differentiate association from risk of CA in the development of CP. DATA SOURCES: PubMed, Cochrane Library, Embase, and bibliographies of original studies were searched by using the keywords (chorioamnionitis) AND ((cerebral palsy) OR brain). STUDY SELECTION: Included studies had to have: (1) controls, (2) criteria for diagnoses, and (3) neurologic follow-up. Studies were categorized based on: (1) finding incidence of CP in a CA population, or risk of CP; and (2) incidence of CA in CP or association with CP. DATA EXTRACTION: Two reviewers independently verified study inclusion and extracted data. RESULTS: Seventeen studies (125 256 CA patients and 5 994 722 controls) reported CP in CA. There was significantly increased CP inpreterm histologic chorioamnionitis (HCA; risk ratio [RR] = 1.34, P < .01), but not in clinical CA (CCA). Twenty-two studies (2513 CP patients and 8135 controls) reported CA in CP. There was increased CCA (RR = 1.43, P < .01), but no increase in HCA in preterm CP. Increased HCA was found (RR = 4.26, P < .05), as well as CCA in term/near-term CP (RR = 3.06, P < .01). CONCLUSIONS: The evidence for a causal or associative role of CA in CP is weak. Preterm HCA may be a risk factor for CP, whereas CCA is not. An association with term and preterm CP was found for CCA, but only with term CP for HCA. PMID:28814548

Can ebselen prevent cisplatin-induced ovarian damage?

PubMed

Soyman, Zeynep; Uzun, Hafize; Bayindir, Nihan; Esrefoglu, Mukaddes; Boran, Birtan

2018-06-01

The occurrence of ovarian damage is a major shortcoming in treating tumors with cisplatin (CP). The present study investigates the beneficial effects of ebselen-a seleno-organic compound with antioxidant and antiinflammatory properties-vis-à-vis CP-induced ovarian damage. Twenty-eight adult female rats were divided into four study groups. Group 1 received no treatment. The rats in Groups 2, 3, and 4 were intraperitoneally administered CP (2 mg/kg/day) twice per week, for 5 weeks. Those in Group 2 received 0.3 ml saline (0.9% NaCl) intraperitoneally 60 min before each CP treatment, while those in Group 3 received 0.2 ml dimethyl sulfoxide (DMSO) and 0.3 ml saline intraperitoneally 60 min before each CP treatment. The rats in Group 4 were pretreated with an intraperitoneal injection of 15 mg/kg/day ebselen 60 min before each CP treatment. Ovarian tissue malondialdehyde (MDA), total nitric oxide (NOx), glutathione (GSH), Cu/Zn-superoxide dismutase (Cu/Zn-SOD), and catalase levels, as well as histopathological damage scores (HDSs) and serum antimullerian hormone (AMH) levels, were assessed. Cu/Zn-SOD and GSH levels were significantly higher, and MDA and NOx levels significantly lower, in Group 4 than in Groups 2 and 3. Pretreatment with ebselen significantly improved serum AMH levels, relative to Groups 2 and 3. Additionally, HDS values were significantly lower in Group 4 than in Groups 2 and 3. Our results from using an experimental rat model of CP chemotherapy suggest that ebselen use may ameliorate ovarian damage by preventing oxidative injury.

Synthesis and reactions of nickel and palladium carbon-bound enolate complexes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Burkhardt, E.R.; Bergman, R.G.; Heathcock, C.H.

1990-01-01

Nickel and palladium carbon-bound enolates of the general formula {eta}{sup 5}-C{sub 5}R{sub 5}(Ph{sub 3}P)MCHR{prime}COR{double prime} (R = H, CH{sub 3}; R{prime} = H, CH{sub 3}; R{double prime} = t-Bu, Ph, O-t-Bu) were prepared. Cp{sup *}(Ph{sub 3}P)NiCH{sub 2}CO{sub 2}-t-Bu (1e) was characterized by X-ray diffraction. Compound 1e crystallizes in the monoclinic space group P2{sub 1}/n with unit-cell dimensions a = 13.6110 (20) {angstrom}, b = 12.7454 (13) {angstrom}, c = 17.8571 (23) {angstrom}, {beta} = 105.544 (11){degree}, Z = 4, observed data 4,091, R = 4.53%, and R{sub w} = 4.19%. Reactions of these nickel and palladium enolates with aldehydes andmore » other electrophilic reagents were examined. The nickel ketone enolates were shown to react with 2 equiv of benzaldehyde to deliver products resulting from a Tischtschenko-type oxidation/reduction process. Cp(Ph{sub 3}P)NiCH{sub 2}CO-t-Bu reacts with phosphines (L) to yield paramagnetic nickel(I) complexes of general formula Cp(L){sub 2}Ni.« less

Short communication: Evaluation of acid-insoluble ash and indigestible neutral detergent fiber as total-tract digestibility markers in dairy cows fed corn silage-based diets.

PubMed

Lee, C; Hristov, A N

2013-08-01

The objective of this experiment was to evaluate acid-insoluble ash (AIA) and indigestible NDF (iNDF) as intrinsic digestibility markers in comparison with total fecal collection (TC) in dairy cows fed corn silage- and alfalfa haylage-based diets. The experiment was part of a larger experiment, which involved 8 Holstein cows [102±28.4 d in milk, 26.4±0.27 kg/d of dry matter (DM) intake, and 43±5.3 kg/d milk yield]. The experimental design was a replicated 4×4 Latin square with the following treatments: metabolizable protein (MP)-adequate diet [15.6% crude protein (CP); high-CP], MP-deficient diet (14.0% CP; low-CP), and 2 other low-CP diets supplemented (top-dressed) with ruminally protected Lys or Lys and Met. Data for the 3 low-CP diets were combined for this analysis. Total feces were collected for 5 consecutive days during each period to estimate total-tract apparent digestibility. Digestibility was also estimated using AIA (digestion with 2 N HCl) and iNDF (12-d ruminal incubation in 25-μm-pore-size bags). Significant diet × digestibility method interactions were observed for fecal output of nutrients and digestibility. Fecal output of nutrients estimated using AIA or iNDF was lower compared with TC and fecal output of DM, organic matter, and CP tended to be higher for iNDF compared with AIA for the high-CP diet. For the low-CP diet, however, fecal output of all nutrients was lower for AIA compared with TC and was higher for iNDF compared with TC. Data from this experiment showed that, compared with TC, AIA underestimated fecal output and overestimated digestibility, particularly evident with the fiber fractions and the protein-deficient diet. Compared with TC, fecal output was overestimated and digestibility of the low-CP diet was underestimated when iNDF was used as a marker, although the magnitude of the difference was smaller compared with that for AIA. In the conditions of the current study, iNDF appeared to be a more reliable digestibility marker than AIA in terms of detecting dietary differences in apparent digestibility of some nutrients, but significant diet × marker interactions existed that need to be considered when estimating total-tract digestibility using intrinsic markers. Copyright © 2013 American Dairy Science Association. Published by Elsevier Inc. All rights reserved.

Quantification of genetically modified soya using strong anion exchange chromatography and time-of-flight mass spectrometry.

PubMed

Chang, Po-Chih; Reddy, P Muralidhar; Ho, Yen-Peng

2014-09-01

Stable-isotope dimethyl labeling was applied to the quantification of genetically modified (GM) soya. The herbicide-resistant gene-related protein 5-enolpyruvylshikimate-3-phosphate synthase (CP4 EPSPS) was labeled using a dimethyl labeling reagent, formaldehyde-H2 or -D2. The identification and quantification of CP4 EPSPS was performed using matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS). The CP4 EPSPS protein was separated from high abundance proteins using strong anion exchange chromatography and sodium dodecyl sulfate-polyacrylamide gel electrophoresis. Then, the tryptic peptides from the samples and reference were labeled with formaldehyde-H2 and formaldehyde-D2, respectively. The two labeled pools were mixed and analyzed using MALDI-MS. The data showed a good correlation between the peak ratio of the H- and D-labeled peptides and the GM soya percentages at 0.5, 1, 3, and 5 %, with R (2) of 0.99. The labeling reagents are readily available. The labeling experiments and the detection procedures are simple. The approach is useful for the quantification of GM soya at a level as low as 0.5 %.

A comparison of the fatigue behavior of cast Ti-7.5Mo with c.p. titanium, Ti-6Al-4V and Ti-13Nb-13Zr alloys.

PubMed

Lin, Chia-Wei; Ju, Chien-Ping; Chern Lin, Jiin-Huey

2005-06-01

The purpose of the present study is to compare the high-cycle fatigue behavior of newly developed Ti-7.5Mo alloy with that of c.p. Ti, Ti-13Nb-13Zr and Ti-6Al-4V alloys in their as-cast state. Experimental results indicate that Ti-6Al-4V and c.p. Ti have higher stress-controlled fatigue resistance but lower strain-controlled fatigue resistance than Ti-7.5Mo and Ti-13Nb-13Zr. Among four materials Ti-7.5Mo demonstrates the best strain-controlled fatigue performance. The fracture surfaces of the present materials are comprised of three morphologically distinct zones: crack initiation zone, crack propagation zone, and the final-stage overload zone. The fatigue cracks almost always initiate from casting-induced surface/subsurface pores. A river pattern is observed in the propagation zone. In the overload zone dimples are typically observed. Three factors most significantly affecting the fatigue performance of the present materials are the presence of the casting-induced surface/subsurface pores; the location of the pores; and the inherent mechanical properties of the materials.

Effect of dietary protein level and source on bone mineralization in rats.

PubMed

Gralak, M A; Piastowska, A W; Leontowicz, H; Leontowicz, M; Antczak, A; Kulasek, G W; Szara, T; Narojek, T

2004-01-01

Bone mineralization was studied in rats. Animals were divided into three feeding groups: LCP - diet with 13.5% crude protein in DM (5% of gluten, 10% of casein), HCP - diet with 21.2% CP in DM (8% of gluten, 10% of casein), and LSM - diet based on grain meals and meat-bone meal (21% CP in DM). After 28 days feeding, animals were euthanased by cervical dislocation and femur bones were collected, weighed and kept frozen until analyses. Diets with 21% protein (HCP, LSM) significantly increased weight of femur bones. Despite of the substantially higher ash level (7.1%) in the LSM diet than in the LCP diet (3.4%), rats of both groups had the similar bone concentration of Ca (15.7 +/- 1.1 vs. 17.4 +/- 1.1 g/kg) and Zn (178.7 +/- 7.9 vs. 173.0 +/- 8.5 mg/kg). However bone density in LSM rats was significantly higher than in LCP ones. Although rats fed HCP diet had intermediate bone density, the bone concentration of Ca (11.4 +/- 0.5 g/kg) and Zn (145.1 +/- 2.9 mg/kg) was significantly lower, than in animals fed LCP and LSM diets. This was related to the very wide protein/calcium (37:1 g/g) and protein/zinc (5.3:1 g/mg) ratios in HCP diet. Those ratios were narrowest in the LSM diet: 16.2:1 (CP/Ca) and 2.6:1 (CP/Zn). It can be conluded that protein/mineral ratio in a diet is a very important factor in bone development, besides dietary protein and ash contents itselves.

Effect of various tooth-whitening products on enamel microhardness.

PubMed

Grobler, S R; Majeed, A; Moola, M H

2009-11-01

The purpose of this in vitro study was to evaluate the effect of various tooth-whitening products containing carbamide peroxide (CP) or hydrogen peroxide (HP), on enamel microhardness. Enamel blocks were exposed to: Nite White ACP 10% CP (Group 2, n=10); Yotuel Patient 10% CP (Group 3, n=10); Opalescence PF 10% CP (Group 4, n=10); Opalescence PF 20% CP (Group 5, n=10); Opalescence Treswhite Supreme 10% HP (Group 6, n=10); Yotuel 10 Minutes 30% CP (Group 7, n=10); Opalescence Quick 45% CP (Group 8, n=10), Yotuel Special 35% HP (Group 9, n=10), Opalescence Boost 38% HP (Group 10, n=10) according to the instructions of the manufacturers. The control (Group 1, n=10) was enamel blocks kept in artificial saliva at 37 degrees C without any treatment. The microhardness values were obtained before exposure and after a 14-day treatment period. Specimens were kept in artificial saliva at 37 degrees C between treatments. Data were analysed using Kruskal-Wallis one-way ANOVA and Tukey-Kramer Multiple Comparison Test. Indent marks on the enamel blocks were also examined under the Scanning Electron Microscope. All whitening products decreased enamel microhardness except group 10 but only Groups 2, 3, 4, 5 and 7 showed significant decrease in enamel microhardness as compared to the control group (p < 0.05). Groups 2, 3 and 7 differed significantly from all the other groups (p < 0.05). The highest damage was recorded for Group 2 (Nite White ACP 10% CP), which differed significantly from Groups 3 and 7. SEM images also showed damage to enamel. All products tested in this study decreased enamel microhardness except Opalescence Boost 38% HP. The products containing carbamide peroxide were more damaging to enamel because of the longer application times. Nite White ACP 10% CP showed the highest reduction in enamel microhardness as compared to other products tested.

A LINE-1 Insertion in DLX6 Is Responsible for Cleft Palate and Mandibular Abnormalities in a Canine Model of Pierre Robin Sequence

PubMed Central

Wolf, Zena T.; Leslie, Elizabeth J.; Arzi, Boaz; Jayashankar, Kartika; Karmi, Nili; Jia, Zhonglin; Rowland, Douglas J.; Young, Amy; Safra, Noa; Sliskovic, Saundra; Murray, Jeffrey C.; Wade, Claire M.; Bannasch, Danika L.

2014-01-01

Cleft palate (CP) is one of the most commonly occurring craniofacial birth defects in humans. In order to study cleft palate in a naturally occurring model system, we utilized the Nova Scotia Duck Tolling Retriever (NSDTR) dog breed. Micro-computed tomography analysis of CP NSDTR craniofacial structures revealed that these dogs exhibit defects similar to those observed in a recognizable subgroup of humans with CP: Pierre Robin Sequence (PRS). We refer to this phenotype in NSDTRs as CP1. Individuals with PRS have a triad of birth defects: shortened mandible, posteriorly placed tongue, and cleft palate. A genome-wide association study in 14 CP NSDTRs and 72 unaffected NSDTRs identified a significantly associated region on canine chromosome 14 (24.2 Mb–29.3 Mb; praw = 4.64×10−15). Sequencing of two regional candidate homeobox genes in NSDTRs, distal-less homeobox 5 (DLX5) and distal-less homeobox 6 (DLX6), identified a 2.1 kb LINE-1 insertion within DLX6 in CP1 NSDTRs. The LINE-1 insertion is predicted to insert a premature stop codon within the homeodomain of DLX6. This prompted the sequencing of DLX5 and DLX6 in a human cohort with CP, where a missense mutation within the highly conserved DLX5 homeobox of a patient with PRS was identified. This suggests the involvement of DLX5 in the development of PRS. These results demonstrate the power of the canine animal model as a genetically tractable approach to understanding naturally occurring craniofacial birth defects in humans. PMID:24699068

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sanuki, Naoko; Takeda, Atsuya; Oku, Yohei

Purpose: Focal liver reaction (FLR) appears on radiographic images after stereotactic ablative body radiation therapy (SABR) in patients with hepatocellular carcinoma (HCC) and chronic liver disease. We investigated the threshold dose (TD) of FLR and possible factors affecting the TD on gadoxetate acid (Gd-EOB-DTPA)-enhanced magnetic resonance imaging (MRI). Methods and Materials: In 50 patients who were treated with SABR for small HCC and followed up by MRI for >6 months, FLR, seen as a hypointense area, was evaluated on the hepatobiliary phase of Gd-EOB-DTPA-enhanced MRI. The follow-up MRI with the largest extent of FLR was fused to the planning computedmore » tomography (CT) image, and patients with good image fusion concordance were eligible. After delineating the border of the FLR manually, a dose–volume histogram was used to identify the TD for the FLR. Clinical and volumetric factors were analyzed for correlation with the TD. Results: A total of 45 patients were eligible for analysis with a median image fusion concordance of 84.9% (range, 71.6-95.4%). The median duration between SABR and subsequent hepatobiliary phase MRI with the largest extent of FLR was 3 months (range, 1-6 months). The median TD for FLR was 28.0 Gy (range, 22.3-36.4 Gy). On univariate analysis, pre-treatment Child-Pugh (CP) score and platelet count were significantly correlated with the TD. On multiple linear regression analysis, CP score was the only parameter that predicted TD. Median TDs were 30.5 Gy (range, 26.2.3-36.4 Gy) and 25.2 Gy (range, 22.3-27.5 Gy) for patients with CP-A and CP-B disease, respectively. Conclusion: The TD was significantly correlated with baseline liver function. We propose 30 Gy for CP-A disease and 25 Gy for CP-B disease in 5 fractions as TDs for FLR after SABR for patients with HCC and chronic liver disease. Use of these TDs will help to predict potential loss of liver tissue after SABR.« less

Splitting a C-O bond in dialkylethers with bis(1,2,4-tri-t-butylcyclopentadienyl) cerium-hydride does not occur by a sigma-bond metathesis pathway: a combined experimental and DFT computational study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Werkema, Evan; Yahia, Ahmed; Maron, Laurent

2010-04-06

Addition of diethylether to [1,2,4(Me3C)3C5H2]2CeH, abbreviated Cp'2CeH, gives Cp'2CeOEt and ethane. Similarly, di-n-propyl- or di-n-butylether gives Cp'2Ce(O-n-Pr) and propane or Cp'2Ce(O-n-Bu) and butane, respectively. Using Cp'2CeD, the propane and butane contain deuterium predominantly in their methyl groups. Mechanisms, formulated on the basis of DFT computational studies, show that the reactions begin by an alpha or beta-CH activation with comparable activation barriers but only the beta-CH activation intermediate evolves into the alkoxide product and an olefin. The olefin then inserts into the Ce-H bond forming the alkyl derivative, Cp'2CeR, that eliminates alkane. The alpha-CH activation intermediate is in equilibrium with themore » starting reagents, Cp'2CeH and the ether, which accounts for the deuterium label in the methyl groups of the alkane. The one-step sigma-bond metathesis mechanism has a much higher activation barrier than either of the two-step mechanisms.« less

First observation of CP violation in B¯ 0 → D (*) CP h 0 decays by a combined time-dependent analysis of BaBar And Belle Data

DOE Office of Scientific and Technical Information (OSTI.GOV)

Abdesselam, A.

We report a measurement of the time-dependent CP asymmetry of B¯ 0 → D (*) CPh 0 decays, where the light neutral hadron h 0 is a π 0, η, or ω meson, and the neutral D meson is reconstructed in the CP eigenstates K +K –, K 0 Sπ 0, or K 0 Sω. The measurement is performed combining the final data samples collected at the Υ(4S) resonance by the BABAR and Belle experiments at the asymmetric-energy B factories PEP-II at SLAC and KEKB at KEK, respectively. The data samples contain (471±3)×10 6 BB¯ pairs recorded by the BABARmore » detector and (772±11)×10 6 BB¯ pairs recorded by the Belle detector. We measure the CP asymmetry parameters –ηfS=+0.66±0.10(stat)±0.06(syst) and C=–0.02±0.07(stat)±0.03(syst). These results correspond to the first observation of CP violation in B¯ 0 → D (*) CPh 0 decays. As a result, the hypothesis of no mixing-induced CP violation is excluded in these decays at the level of 5.4 standard deviations.« less

Nitrogen metabolism and route of excretion in beef feedlot cattle fed barley-based backgrounding diets varying in protein concentration and rumen degradability.

PubMed

Koenig, K M; Beauchemin, K A

2013-05-01

The objectives of the study were to characterize the effects of CP concentration and ruminal degradability of barley-based backgrounding diets on route and chemical form of N excretion, ruminal fermentation, microbial protein synthesis, and nutrient digestion in beef cattle. Four Angus heifers (479 ± 14.6 kg average BW) with ruminal and duodenal cannulas were used in an experiment designed as a 4 × 4 Latin square. The basal diet consisted of 54% barley silage and 46% barley grain-based concentrate (DM basis). Dietary treatments included the basal diet with no added protein (12% CP) or diets formulated to contain 14% CP by supplementation with urea (UREA), urea and canola meal (UREA+CM), or urea, corn gluten meal, and xylose-treated soybean meal (UREA+CGM+xSBM). The amount of feed offered was restricted to 95% of ad libitum intake. There was no effect of the diets on DMI (P = 0.38), and therefore, N intake was less (P < 0.05) in heifers fed the 12% CP diets than the 14% CP diets. Fecal N output was not affected by the diet (P = 0.15), but urine N (P < 0.10) and urea N output were greater (P < 0.05) in heifers fed the 14% CP than the 12% CP diets. There was no effect of CP degradability (P > 0.10) on the amount of urine N output. Urine N output was 38.9 and 45.1 ± 5.50% of N intake in heifers fed the 12% CP and 14% CP diets (P < 0.05), respectively. Urea N, the form of N most susceptible to NH3-N volatilization and loss, was the major form of N in urine (75.5% in heifers fed the 12% CP diet and 81.4 ± 1.7% in heifers fed the 14% CP diets; P < 0.05). Supplemental RDP (UREA+CM) and RUP combined with urea (UREA+CGM+xSBM) to provide 14% CP increased (P < 0.05) ruminal NH3-N but had no effect on ruminal peptide N (P = 0.62) and free AA N (P = 0.18) concentration, the flow of microbial (P = 0.34) and feed (P = 0.55) N, and ruminal (starch, P = 0.11; NDF, P = 0.78) and total tract nutrient digestibility (OM, P = 0.21; starch, P = 0.16). Supplementation of barley-based backgrounding diets containing 12% CP with NPN alone or combined with ruminally degradable and undegradable true protein to attain 14% CP had no effect on fecal N output, but urine N and urea N increased irrespective of protein source. In addition, the ruminal degradability of the protein sources did not influence the composition of protein flowing to the intestine and site and extent of nutrient digestibility.

Molybdenum Hydride and Dihydride Complexes Bearing Diphosphine Ligands with a Pendant Amine: Formation of Complexes With Bound Amines

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Shaoguang; Bullock, R. Morris

2015-07-06

CpMo(CO)(PNP)H complexes (PNP = (R2PCH2)2NMe, R = Et or Ph) were synthesized by displacement of two CO ligands of CpMo(CO)3H by the PNP ligand; these complexes were characterized by IR and variable temperature 1H and 31P NMR spectroscopy. CpMo(CO)(PNP)H complexes are formed as mixture of cis and trans-isomers. Both cis-CpMo(CO)(PEtNMePEt)H and trans-CpMo(CO)(PPhNMePPh)H were analyzed by single crystal X-ray diffraction. Electrochemical oxidation of CpMo(CO)(PEtNMePEt)H and CpMo(CO)(PPhNMePPh)H in CH3CN are both irreversible at slow scan rates and quasi-reversible at higher scan rates, with E1/2 = -0.36 V (vs. Cp2Fe+/0) for CpMo(CO)(PEtNMePEt)H and E1/2 = -0.18 V for CpMo(CO)(PPhNMePPh)H. Hydride abstraction from CpMo(CO)(PNP)Hmore » with [Ph3C]+[A]- (A = B(C6F5)4 or BArF4; [ArF = 3,5-bis(trifluoromethyl)phenyl]) afforded “tuck-in” [CpMo(CO)(κ3-PNP)]+ complexes that feature the amine bound to the metal. Displacement of the κ3 Mo-N bond by CD3CN gives [CpMo(CO)(PNP)(CD3CN)]+. The kinetics of this reaction were studied by NMR spectroscopy, providing the activation parameters ΔH‡ = 22.1 kcal/mol, ΔS‡ = 1.89 cal/(mol·K), Ea = 22.7 kcal/mol. Protonation of CpMo(CO)(PEtNMePEt)H affords [CpMo(CO)(κ2-PEtNMePEt)(H)2]+ as a Mo dihydride complex, which loses H2 to generate [CpMo(CO)(κ3-PEtNMePEt)]+ at room temperature. CpMo(CO)(dppp)H (dppp = 1,2-bis(diphenylphosphino)propane) was studied as a Mo diphosphine analogue without a pendant amine, and the product of protonation of this complex gives [CpMo(CO)(dppp)(H)2]+. Our results show that the pendant amine has a strong driving force to form stable “tuck-in” [CpMo(CO)(κ3-PNP)]+ complexes, and also promotes hydrogen elimination from [CpMo(CO)(PNP)(H)2]+ complexes by formation of Mo-N dative bond. We thank the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences for support. Pacific Northwest National Laboratory is operated by Battelle for the U.S. Department of Energy. We thank Monte Helm, Elliott Hulley and Deanna Miller for help on the crystallography, and Ming Fang for assistance on the electrochemical experiments.« less

TREM-1 expression in craniopharyngioma and Rathke's cleft cyst: its possible implication for controversial pathology.

PubMed

Liu, Yi; Wang, Chao-Hu; Li, Dan-Ling; Zhang, Shi-Chao; Peng, Yu-Ping; Peng, Jun-Xiang; Song, Ye; Qi, Song-Tao; Pan, Jun

2016-08-02

Whether a mixed type of craniopharyngioma (CP) exists and whether papillary craniopharyngioma (pCP) is on a histopathological continuum with Rathke's cleft cyst (RCC) remain controversial. Herein, we examined the expression and localization of β-catenin, BRAF p.V600E (V600E), and triggering receptor expressed on myeloid cells-1 (TREM-1) in 58 samples including 20 pCPs, 26 adamantinomatous craniopharyngiomas (aCP), and 12 RCCs. Five aCPs were diagnosed with mixed type CPs and the remaining 21 cases were pure aCPs. Four of the 12 RCCs presented with significant squamous epithelium (SE). V600E immunoreactivity was observed in all pCPs in the cytoplasm, but not in the nuclei. aCPs and RCCs, including mixed type CP, did not express V600E. Nuclear β-catenin translocation was detected exclusively in aCPs. TREM-1 was expressed in pCPs. Additionally, TREM-1 expression was detected in the SE of 5 "mixed type" CPs, while it was absent in pure aCPs. TREM-1 was expressed in 4 RCCs with SE, but not in the remaining 8 RCCs. TREM-1 mRNA levels were compared in cultured pCP and aCP cells. TREM-1 mRNA level was significantly (p < 0.001; up to 4.045 fold) higher in pCPs than in aCPs. Western blotting revealed a significantly (p < 0.001; up to 7.19 fold) lower level of TREM-1 expression in aCP cells compared to that in pCP cells. Our findings further supported that RCC and pCP may represent two ends of a morphological spectrum. A variant showing overlapping histological features of aCP and pCP should not be considered as a mixed type.

Impact of vasomotion type on prognosis of coronary artery spasm induced by acetylcholine provocation test of left coronary artery.

PubMed

Lee, Eun Mi; Choi, Man Ho; Seo, Hong Seog; Kim, Hyun Ki; Kim, Nam-Ho; Choi, Cheol Ung; Kim, Jin Won; Lim, Hong Euy; Kim, Eung Ju; Rha, Seung-Woon; Park, Chang Gyu; Oh, Dong Joo

2017-02-01

The impact of vasomotion types on long-term clinical outcomes in patients with coronary artery spasm (CAS) induced by the acetylcholine provocation test (ACH-test) remains unclear. We evaluated 4644 consecutive patients with typical resting chest pain (CP), but no angiographically significant coronary artery lesion (<50% stenosis), who underwent an ACH-test. According to their vasomotor response, patients were categorized into four types: normal vasomotion (no CP, no ischemic electrocardiographic changes, and no vasoconstriction), microvascular spasm (CP with <75% vasoconstriction but with CP relief after nitroglycerin infusion), epicardial spasm (CP with ≥75% vasoconstriction), and ACH-test inconclusive (vasoconstriction and/or electrocardiographic changes, but no CP). We investigated CP recurrence requiring follow-up angiography and major adverse cardiovascular events (MACEs) during 5 years. CP recurred in 7.9% of patients and was more frequent in abnormal vasomotion types (normal vasomotion, microvascular spasm, epicardial spasm, and inconclusive type: 5.4%, 9.8%, 10.9%, and 8.2%, respectively, log-rank p = 0.009). In multivariate analysis adjusted for medication use after the ACH-test, vasomotion subtype was not an independent predictor, whereas male sex, fixed lesion on baseline angiography, and medications including calcium channel blockers (CCBs), nitrates, and statins were independent positive predictors for recurrent CP. Alcohol consumption at the initial interview was a negative predictor. MACEs were observed in 1.6%, and the incidence was similar among subtypes (p = 0.421). Recurrent CP and long-term outcomes are independent of vasomotion subtypes, but long-term use of CCBs, nitrates, and statins is a significant predictor for recurrent CP. Copyright © 2016 Elsevier Ireland Ltd. All rights reserved.

CenteringPregnancy-Africa: a pilot of group antenatal care to address Millennium Development Goals.

PubMed

Patil, Crystal L; Abrams, Elizabeth T; Klima, Carrie; Kaponda, Chrissie P N; Leshabari, Sebalda C; Vonderheid, Susan C; Kamanga, Martha; Norr, Kathleen F

2013-10-01

severe health worker shortages and resource limitations negatively affect quality of antenatal care (ANC) throughout sub-Saharan Africa. Group ANC, specifically CenteringPregnancy (CP), may offer an innovative approach to enable midwives to offer higher quality ANC. our overarching goal was to prepare to conduct a clinical trial of CenteringPregnancy-Africa (CP-Africa) in Malawi and Tanzania. In Phase 1, our goal was to determine the acceptability of CP as a model for ANC in both countries. In Phase 2, our objective was to develop CP-Africa session content consistent with the Essential Elements of CP model and with national standards in both Malawi and Tanzania. In Phase 3, our objective was to pilot CP-Africa in Malawi to determine whether sessions could be conducted with fidelity to the Centering process. Phases 1 and 2 took place in Malawi and Tanzania. Phase 3, the piloting of two sessions of CP-Africa, occurred at two sites in Malawi: a district hospital and a small clinic. we used an Action Research approach to promote partnerships among university researchers, the Centering Healthcare Institute, health care administrators, health professionals and women attending ANC to develop CP-Africa session content and pilot this model of group ANC. for Phases 1 and 2, members of the Ministries of Health, health professionals and pregnant women in Malawi and Tanzania were introduced to and interviewed about CP. In Phase 2, we finalised CP-Africa content and trained 13 health professionals in the Centering Healthcare model. In Phase 3, we conducted a small pilot with 24 pregnant women (12 at each site). participants enthusiastically embraced CP-Africa as an acceptable model of ANC health care delivery. The CP-Africa content met both CP and national standards. The pilot established that the CP model could be implemented with process fidelity to the 13 Essential Elements. Several implementation challenges and strategies to address these challenges were identified. preliminary data suggest that CP-Africa is feasible in resource-constrained, low-literacy, high-HIV settings in sub-Saharan Africa. By improving the quality of ANC delivery, midwives have an opportunity to make a contribution towards Millennium Development Goals (MDG) targeting improvements in child, maternal and HIV-related health outcomes (MDGs 4, 5 and 6). A clinical trial is needed to establish efficacy. CP-Africa also has the potential to reduce job-related stress and enhance job satisfaction for midwives in low income countries. If CP can be transferred with fidelity to process in sub-Saharan Africa and retain similar results to those reported in clinical trials, it has the potential to benefit pregnant women and their infants and could make a positive contribution to MGDs 4, 5 and 6. © 2013 Elsevier Ltd. All rights reserved.

Search for the CP-Violating Decays Υ(4S)→B0B¯0→J/ψKS0+J/ψ(ηc)KS0

NASA Astrophysics Data System (ADS)

Tajima, O.; Hazumi, M.; Adachi, I.; Aihara, H.; Aulchenko, V.; Aushev, T.; Bakich, A. M.; Barberio, E.; Bay, A.; Bedny, I.; Bhardwaj, V.; Bitenc, U.; Bozek, A.; Bračko, M.; Browder, T. E.; Chang, M.-C.; Chang, P.; Chen, A.; Chen, K.-F.; Chen, W. T.; Cheon, B. G.; Chiang, C.-C.; Chistov, R.; Cho, I.-S.; Choi, Y.; Choi, Y. K.; Dalseno, J.; Danilov, M.; Dash, M.; Drutskoy, A.; Eidelman, S.; Epifanov, D.; Go, A.; Gokhroo, G.; Golob, B.; Haba, J.; Hayasaka, K.; Hayashii, H.; Heffernan, D.; Hokuue, T.; Hoshi, Y.; Hou, W.-S.; Hsiung, Y. B.; Hyun, H. J.; Iijima, T.; Ikado, K.; Inami, K.; Ishikawa, A.; Ishino, H.; Itoh, R.; Iwasaki, M.; Iwasaki, Y.; Joshi, N. J.; Kah, D. H.; Kaji, H.; Kang, J. H.; Kataoka, S. U.; Kawai, H.; Kawasaki, T.; Kichimi, H.; Kim, H. J.; Kim, H. O.; Kim, S. K.; Kim, Y. J.; Kinoshita, K.; Korpar, S.; Križan, P.; Krokovny, P.; Kumar, R.; Kuo, C. C.; Kwon, Y.-J.; Lange, J. S.; Lee, J. S.; Lee, M. J.; Lee, S. E.; Lesiak, T.; Li, J.; Lin, S.-W.; Liventsev, D.; Mandl, F.; Marlow, D.; McOnie, S.; Medvedeva, T.; Mitaroff, W.; Miyabayashi, K.; Miyake, H.; Miyata, H.; Mizuk, R.; Mohapatra, D.; Nagasaka, Y.; Nakano, E.; Nakao, M.; Nishida, S.; Nitoh, O.; Noguchi, S.; Nozaki, T.; Ogawa, S.; Ohshima, T.; Okuno, S.; Ozaki, H.; Pakhlov, P.; Pakhlova, G.; Park, C. W.; Park, H.; Pestotnik, R.; Piilonen, L. E.; Sahoo, H.; Sakai, Y.; Schneider, O.; Sekiya, A.; Senyo, K.; Sevior, M. E.; Shapkin, M.; Shen, C. P.; Shibuya, H.; Shiu, J.-G.; Shwartz, B.; Singh, J. B.; Sokolov, A.; Somov, A.; Stanič, S.; Starič, M.; Sumisawa, K.; Sumiyoshi, T.; Takasaki, F.; Tanaka, M.; Taylor, G. N.; Teramoto, Y.; Trabelsi, K.; Uehara, S.; Ueno, K.; Uglov, T.; Unno, Y.; Uno, S.; Urquijo, P.; Usov, Y.; Varner, G.; Varvell, K. E.; Vervink, K.; Villa, S.; Vinokurova, A.; Wang, C. C.; Wang, C. H.; Wang, M.-Z.; Wang, P.; Watanabe, Y.; Wedd, R.; Won, E.; Yabsley, B. D.; Yamaguchi, A.; Yamashita, Y.; Yamauchi, M.; Yuan, C. Z.; Yusa, Y.; Zhang, C. C.; Zhang, Z. P.; Zhilich, V.; Zhulanov, V.; Zupanc, A.

2007-11-01

We report the first search for CP-violating decays of the Υ(4S) using a data sample that contains 535×106 Υ(4S) mesons with the Belle detector at the KEKB asymmetric-energy e+e- collider. A partial reconstruction technique is employed to enhance the signal sensitivity. No significant signals were observed. We obtain an upper limit of 4×10-7 at the 90% confidence level for the branching fractions of the CP violating modes, Υ(4S)→B0B¯0→J/ψKS0+J/ψ(ηc)KS0. Extrapolating the result, we find that an observation with 5σ significance is expected with a 30ab-1 data sample, which is within the reach of a future super B factory.

Synthetic Poly(L-Glutamic Acid)-conjugated CpG Exhibits Antitumor Efficacy With Increased Retention in Tumor and Draining Lymph Nodes After Intratumoral Injection in a Mouse Model of Melanoma.

PubMed

Ma, Qing; Zhou, Dapeng; DeLyria, Elizabeth S; Wen, Xiaoxia; Lu, Wei; Thapa, Prakash; Liu, Chengwen; Li, Dan; Bassett, Roland L; Overwijk, Willem W; Hwu, Patrick; Li, Chun

2017-01-01

There is an urgent need for new clinically applicable drug-delivery methods to enhance accumulation of immune-activating drugs in tumors. We synthesized a poly(L-glutamic acid)-CpG ODN2216 conjugate (PG-CpG) and injected it intratumorally into C57BL/6 mice bearing subcutaneous B16-ovalbumin melanoma. PG-CpG elicited the same potent antitumoral activity as CpG with respect to reducing tumor growth and triggering antigen-specific CD8 T-cell responses in this well-established solid tumor model. Moreover, PG-CpG was retained significantly longer in both tumor and draining lymph nodes than was free CpG after intratumoral injection. Specifically, 48 hours after injection, 26.5%±16.9% of the injected PG-CpG dose versus 4.72%±2.61% of free CpG remained at the tumor, and 1.53%±1.22% of the injected PG-CpG versus 0.37%±0.33% of free CpG was retained in the draining inguinal lymph nodes. These findings indicate that PG is an effective synthetic polymeric carrier for delivery of immunostimulatory agents to tumors and lymph nodes.

[Relationship between C-reactive protein gene polymorphaisms and chronic periodontitis].

PubMed

Liu, Juan; Meng, Shu; Ding, Yi; Wu, Ya-fei

2010-06-01

To investigate the relationship between C-reactive protein (CRP) + 1444C/T, CRP+1059G/C polymorphisms and chronic periodontitis (CP) in a Han Chinese population. Clinical periodontal parameters [attachment loss (AL) probing depth (PD) and bleeding on probing (BOP)], and serum CRP levels were examined in CP patients (n = 126) and healthy subjects (n = 113). The mean serum CRP level [(1.74 ± 1.67) mg/L] was significantly higher in the CP group than in the control group [(0.57 ± 0.39) mg/L], P < 0.001. In the control group, serum CRP levels were significantly lower in subjects with the CRP +1059 GC and CC genotypes than those with the CRP +1059 GG genotype (P < 0.01). There was no significant difference between genotypes in the CP group. In CP and the control groups, serum CRP levels were significantly higher in subjects with the CRP + 1444 CT and TT genotypes compared to those with the CRP + 1444 CC genotype (P < 0.5). The percentage of CRP + 1059 C allele was 6.7% (17/252) in the CP group and 4.9% (11/226) in the control group. The percentage of CRP + 1444 T allele was 6.3% (16/252) in the CP group and 5.3% (12/226) in the control group (P > 0.5). There was no significant difference between groups in both allele frequencies (P > 0.5). The association of CRP + 1059G/C, CRP + 1444 C/T polymorphisms with CP was not found in a regression model (P > 0.5). The presence of a CRP + 1059C-allele was associated with lower serum CRP levels and the presence of a CRP + 1444T-allele was associated with higher serum CRP levels. However, the data suggested that CRP + 1059G/C, CRP + 1444 C/T polymorphisms were not significantly associated with serum CRP levels of chronic periodontitis patients in ethnic Han Chinese.

A Copper(II)-Paddlewheel Metal-Organic Framework with Exceptional Hydrolytic Stability and Selective Adsorption and Detection Ability of Aniline in Water.

PubMed

Chen, Ya; Wang, Bin; Wang, Xiaoqing; Xie, Lin-Hua; Li, Jinping; Xie, Yabo; Li, Jian-Rong

2017-08-16

Copper(II)-paddlewheel-based metal-organic frameworks (CP-MOFs) represent a unique subclass of MOFs with highly predictable porous structures, facile syntheses, and functional open metal sites. However, the lack of high hydrolytic stability is an obstacle for CP-MOFs in many practical applications. In this work, we report a new CP-MOF, [Cu 4 (tdhb)] (BUT-155), which is constructed from a judiciously designed carboxylate ligand with high coordination connectivity (octatopic), abundant hydrophobic substituents (six methyl groups), and substituent constrained geometry (tetrahedral backbone), tdhb 8- [H 8 tdhb = 3,3',5,5'-tetrakis(3,5-dicarboxyphenyl)-2,2',4,4',6,6'-hexamethylbiphenyl)]. BUT-155 shows high porosity with a Brunauer-Emmett-Teller surface area of 2070 m 2 /g. Quite interestingly, this CP-MOF retains its structural integrity after being treated in water for 10 days at room temperature or in boiling water for 24 h. To the best of our knowledge, BUT-155 represents the first CP-MOF that is demonstrated to retain its structural integrity in boiling water. The high hydrolytic stability of BUT-155 allowed us to carry out adsorption studies of water vapor and aqueous organic pollutants on it. Water-vapor adsorption reveals a sigmoidal isotherm and a high uptake (46.7 wt %), which is highly reversible and regenerable. In addition, because of the availability of soft-acid-type open Cu(II) sites, BUT-155 shows a high performance for selective adsorption of soft-base-type aniline over water or phenol, and a naked-eye detectable color change for the MOF sample accompanies this. The adsorption selectivity and high adsorption capacity of aniline in BUT-155 are also well-interpreted by single-crystal structures of the water- and aniline-included phases of BUT-155.

Reactivity of yttrium carboxylates toward alkylaluminum hydrides.

PubMed

Schädle, Christoph; Fischbach, Andreas; Herdtweck, Eberhardt; Törnroos, Karl W; Anwander, Reiner

2013-11-25

Yttrocene-carboxylate complex [Cp*2Y(OOCAr(Me))] (Cp*=C5Me5, Ar(Me) =C6H2Me3-2,4,6) was synthesized as a spectroscopically versatile model system for investigating the reactivity of alkylaluminum hydrides towards rare-earth-metal carboxylates. Equimolar reactions with bis-neosilylaluminum hydride and dimethylaluminum hydride gave adduct complexes of the general formula [Cp*2Y(μ-OOCAr(Me))(μ-H)AlR2] (R=CH2SiMe3, Me). The use of an excess of the respective aluminum hydride led to the formation of product mixtures, from which the yttrium-aluminum-hydride complex [{Cp*2Y(μ-H)AlMe2(μ-H)AlMe2(μ-CH3)}2] could be isolated, which features a 12-membered-ring structure. The adduct complexes [Cp*2Y(μ-OOCAr(Me))(μ-H)AlR2] display identical (1)J(Y,H) coupling constants of 24.5 Hz for the bridging hydrido ligands and similar (89)Y NMR shifts of δ=-88.1 ppm (R=CH2SiMe3) and δ=-86.3 ppm (R=Me) in the (89)Y DEPT45 NMR experiments. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A supramolecular Tröger's base derived coordination zinc polymer for fluorescent sensing of phenolic-nitroaromatic explosives in water† †Electronic supplementary information (ESI) available: Spectroscopic (multinuclear NMR, IR HRMS) characterizations, optimized structure, TGA, powder diffraction and fluorescence titration profiles. See DOI: 10.1039/c6sc04367d Click here for additional data file.

PubMed Central

Dabadie, Charlyne; Byrne, Kevin; Savyasachi, Aramballi J.; Umadevi, Deivasigamani; Schmitt, Wolfgang; Kitchen, Jonathan A.

2017-01-01

A V-Shaped 4-amino-1,8-napthalimide derived tetracarboxylic acid linker (L; bis-[N-(1,3-benzenedicarboxylic acid)]-9,18-methano-1,8-naphthalimide-[b,f][1,5]diazocine) comprising the Tröger's base (TB) structural motif was rationally designed and synthesised to access a nitrogen-rich fluorescent supramolecular coordination polymer. By adopting the straight forward precipitation method, a new luminescent nanoscale Zn(ii) coordination polymer (TB-Zn-CP) was synthesized in quantitative yield using Zn(OAc)2·2H2O and tetraacid linker L (1 : 0.5) in DMF at room temperature. The phase-purity of as-synthesised TB-Zn-CP was confirmed by X-ray powder diffraction analysis, infra-red spectroscopy, and elemental analysis. Thermogravimetric analysis suggests that TB-Zn-CP is thermally stable up to 330 °C and the morphological features of TB-Zn-CP was analysed by SEM and AFM techniques. The N2 adsorption isotherm of thermally activated TB-Zn-CP at 77 K revealed a type-II reversible adsorption isotherm and the calculated Brunauer–Emmett–Teller (BET) surface area was found to be 72 m2 g–1. Furthermore, TB-Zn-CP displayed an excellent CO2 uptake capacity of 76 mg g–1 at 273 K and good adsorption selectivity for CO2 over N2 and H2. The aqueous suspension of as-synthesized TB-Zn-CP showed strong green fluorescence (λ max = 520 nm) characteristics due to the internal-charge transfer (ICT) transition and was used as a fluorescent sensor for the discriminative sensing of nitroaromatic explosives. The aqueous suspension of TB-Zn-CP showed the largest quenching responses with high selectivity for phenolic-nitroaromatics (4-NP, 2,4-DNP and PA) even in the concurrent presence of other potentially competing nitroaromatic analytes. The fluorescence titration studies also provide evidence that TB-Zn-CP detects picric acid as low as the parts per billion (26.3 ppb) range. Furthermore, the observed fluorescence quenching responses of TB-Zn-CP towards picric acid were highly reversible. The highly selective fluorescence quenching responses including the reversible detection efficiency make the nanoscale coordination polymer TB-Zn-CP a potential material for the discriminative fluorescent sensing of nitroaromatic explosives. PMID:28572910

Chemistry of the oxophosphinidene ligand. 2. Reactivity of the anionic complexes [MCp{P(O)R*}(CO)(2)](-) (M = Mo, W; R* = 2,4,6-C(6)H(2)(t)Bu(3)) toward electrophiles based on elements different from carbon.

PubMed

Alonso, María; Alvarez, M Angeles; García, M Esther; Ruiz, Miguel A; Hamidov, Hayrullo; Jeffery, John C

2010-12-20

The anionic oxophosphinidene complexes (H-DBU)[MCp{P(O)R*}(CO)(2)] (M = Mo, W; R* = 2,4,6-C(6)H(2)(t)Bu(3); Cp = η(5)-C(5)H(5), DBU = 1,8-diazabicyclo [5.4.0] undec-7-ene) displayed multisite reactivity when faced with different electrophilic reagents. The reactions with the group 14 organochloride compounds ER(4-x)Cl(x) (E = Si, Ge, Sn, Pb) led to either phosphide-like, oxophosphinidene-bridged derivatives [MCp{P(OE')R*}(CO)(2)] (E' = SiMe(3), SiPh(3), GePh(3), GeMe(2)Cl) or to terminal oxophosphinidene complexes [MCp{P(O)R*}(CO)(2)(E')] (E' = SnPh(3), SnPh(2)Cl, PbPh(3); Mo-Pb = 2.8845(4) Å for the MoPb compound). A particular situation was found in the reaction with SnMe(3)Cl, this giving a product existing in both tautomeric forms, with the phosphide-like complex [MCp{P(OSnMe(3))R*}(CO)(2)] prevailing at room temperature and the tautomer [MCp{P(O)R*}(CO)(2)(SnMe(3))] being the unique species present below 203 K in dichloromethane solution. The title anions also showed a multisite behavior when reacting with transition-metal based electrophiles. Thus, the reactions with the complexes [M'Cp(2)Cl(2)] (M' = Ti, Zr) gave phosphide-like derivatives [MCp{P(OM')R*}(CO)(2)] (M = Mo, M' = TiCp(2)Cl, ZrCp(2)Cl; M = W, M' = ZrCp(2)Cl), displaying a bridging κ(1),κ(1)-P,O- oxophosphinidene ligand connecting MCp(CO)(2) and M'Cp(2)Cl metal fragments (W-P = 2.233(1) Å, O-Zr = 2.016(4) Å for the WZr compound]. In contrast, the reactions with the complex [AuCl{P(p-tol)(3)}] gave the metal-metal bonded derivatives trans-[MCp{P(O)R*}(CO)(2){AuP(p-tol)(3)}] (M = Mo, W; Mo-Au = 2.7071(7) Å). From all the above results it was concluded that the terminal oxophosphinidene complexes are preferentially formed under conditions of orbital control, while charge-controlled reactions tend to give derivatives with the electrophilic fragment bound to the oxygen atom of the oxophosphinidene ligand (phosphide-like, oxophosphinidene-bridged derivatives).