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Sample records for biguanide derivatives chemical

  1. Copper-catalyzed arylation of biguanide derivatives via C-N cross-coupling reactions.

    PubMed

    Zhang, Chen; Huang, Bo; Bao, Ai-Qing; Li, Xiao; Guo, Shunna; Zhang, Jin-Quan; Xu, Jun-Zhi; Zhang, Rihao; Cui, Dong-Mei

    2015-12-21

    An efficient copper-catalyzed cross-coupling reaction of biguanide hydrochloride derivatives with both aryl iodides and bromides under mild conditions has been developed. The reaction occurred in good yields and tolerated aryl halides containing functionalities such as nitriles, sulfonamides, ethers, and halogens. Alkyl and cyclic substituted biguanidines were also well tolerated. PMID:26444146

  2. Phagocytosis Affects Biguanide Sensitivity of Acanthamoeba spp.

    PubMed Central

    Noble, Judith A.; Ahearn, Donald G.; Avery, Simon V.; Crow Jr., Sidney A.

    2002-01-01

    The incidence of Acanthamoeba keratitis, a disease associated with contact lens wear, has been in apparent decline with the advent of multipurpose contact lens solutions. The concentrations of the biguanides chlorhexidine digluconate (CHX) and particularly polyhexamethylene biguanide (PHMB) included in multipurpose solutions (MPSs) are sublethal for amoebae. We evaluated by flow cytometry the effects of these two biguanides on phagocytosis of particles and the survival of trophozoites of Acanthamoeba castellanii and A. polyphaga. Trophozoites of A. castellanii and A. polyphaga (106/ml) were exposed to solutions of 5 and 50 μg of PHMB and CHX per ml in the presence and absence of particles (i.e., heat-killed yeasts and bacteria and latex beads). In addition, trophozoites were exposed to particles treated with these concentrations of the two biguanides. In the absence of particles, trophozoites of A. polyphaga appeared to be more resistant to the biguanides than those of A. castellanii. In the presence of particles, the rates of survival of both species were decreased. In most instances, particles treated with sublethal concentrations of both biguanides that were adsorbed onto the particles reduced the incidence of phagocytosis. Particles present in MPSs in contact lens cases may be involved in the decreased incidence of Acanthamoeba keratitis. PMID:12069957

  3. Biguanide related compounds in traditional antidiabetic functional foods.

    PubMed

    Perla, Venu; Jayanty, Sastry S

    2013-06-01

    Biguanides such as metformin are widely used worldwide for the treatment of type-2 diabetes. The identification of guanidine and related compounds in French lilac plant (Galega officinalis L.) led to the development of biguanides. Despite of their plant origin, biguanides have not been reported in plants. The objective of this study was to quantify biguanide related compounds (BRCs) in experimentally or clinically substantiated antidiabetic functional plant foods and potatoes. The corrected results of the Voges-Proskauer (V-P) assay suggest that the highest amounts of BRCs are present in green curry leaves (Murraya koenigii (L.) Sprengel) followed by fenugreek seeds (Trigonella foenum-graecum L.), green bitter gourd (Momordica charantia Descourt.), and potato (Solanum tuberosum L.). Whereas, garlic (Allium sativum L.), and sweet potato (Ipomea batatas (L.) Lam.) contain negligible amounts of BRCs. In addition, the possible biosynthetic routes of biguanide in these plant foods are discussed. PMID:23411283

  4. Effects of 2,4-dimethoxyphenyl biguanide on glutathione system activity in rat tissues in brain ischemia-reperfusion.

    PubMed

    Safonova, O A; Popova, T N; Panchenko, L F

    2011-09-01

    We studied the effects of dimethoxyphenyl biguanide on glutathione peroxidase and glutathione reductase activities, level of reduced glutathione in rat tissues, and activity of some NADPH-regenerating enzymes (glucose-6-phosphate dehydrogenase and NADP-isocitrate dehydrogenase) under conditions of ischemia-reperfusion of the brain. Administration of this biguanide derivative under pathological conditions led to a decrease in the analyzed parameters (elevated under conditions of ischemia-reperfusion) in the serum and brain tissue. The results attest to less pronounced mobilization of the glutathione system (compared to pathological state) due to antioxidant and protective properties of 2,4-dimethoxyphenyl biguanide under conditions of ischemic tissue damage associated with oxidative stress. PMID:22462044

  5. Metformin and Other Biguanides in Oncology: Advancing the Research Agenda

    PubMed Central

    Pollak, Michael

    2010-01-01

    Retrospective studies suggest that diabetics treated with metformin have a substantially reduced cancer burden compared with other diabetics, studies that may be impractical to confirm prospectively. It is unclear if this reflects a chemopreventive effect, an effect on transformed cells, or both. It also remains to be established if these data have relevance to people without diabetes. Laboratory models, however, provide independent impressive evidence for activity of metformin and other biguanides in both cancer treatment and chemoprevention. Investigations of biguanide mechanisms have revealed considerable complexity and have identified important gaps in knowledge that should be addressed to ensure the optimal design of clinical trials of these agents. Such trials may define important new indications of biguanides for the prevention and/or treatment of many common cancers. PMID:20810670

  6. Effects of metformin and other biguanides on oxidative phosphorylation in mitochondria

    PubMed Central

    Bridges, Hannah R.; Jones, Andrew J. Y.; Pollak, Michael N.; Hirst, Judy

    2014-01-01

    The biguanide metformin is widely prescribed for Type II diabetes and has anti-neoplastic activity in laboratory models. Despite evidence that inhibition of mitochondrial respiratory complex I by metformin is the primary cause of its cell-lineage-specific actions and therapeutic effects, the molecular interaction(s) between metformin and complex I remain uncharacterized. In the present paper, we describe the effects of five pharmacologically relevant biguanides on oxidative phosphorylation in mammalian mitochondria. We report that biguanides inhibit complex I by inhibiting ubiquinone reduction (but not competitively) and, independently, stimulate reactive oxygen species production by the complex I flavin. Biguanides also inhibit mitochondrial ATP synthase, and two of them inhibit only ATP hydrolysis, not synthesis. Thus we identify biguanides as a new class of complex I and ATP synthase inhibitor. By comparing biguanide effects on isolated complex I and cultured cells, we distinguish three anti-diabetic and potentially anti-neoplastic biguanides (metformin, buformin and phenformin) from two anti-malarial biguanides (cycloguanil and proguanil): the former are accumulated into mammalian mitochondria and affect oxidative phosphorylation, whereas the latter are excluded so act only on the parasite. Our mechanistic and pharmacokinetic insights are relevant to understanding and developing the role of biguanides in new and existing therapeutic applications, including cancer, diabetes and malaria. PMID:25017630

  7. Chemical Sensors Based on Cyclodextrin Derivatives

    PubMed Central

    Ogoshi, Tomoki; Harada, Akira

    2008-01-01

    This review focuses on chemical sensors based on cyclodextrin (CD) derivatives. This has been a field of classical interest, and is now of current interest for numerous scientists. First, typical chemical sensors using chromophore appended CDs are mentioned. Various “turn-off” and “turn-on” fluorescent chemical sensors, in which fluorescence intensity was decreased or increased by complexation with guest molecules, respectively, were synthesized. Dye modified CDs and photoactive metal ion-ligand complex appended CDs, metallocyclodextrins, were also applied for chemical sensors. Furthermore, recent novel approaches to chemical sensing systems using supramolecular structures such as CD dimers, trimers and cooperative binding systems of CDs with the other macrocycle [2]rotaxane and supramolecular polymers consisting of CD units are mentioned. New chemical sensors using hybrids of CDs with π-conjugated polymers, peptides, DNA, nanocarbons and nanoparticles are also described in this review.

  8. Polyhexamethylene biguanide functionalized cationic silver nanoparticles for enhanced antimicrobial activity

    PubMed Central

    2012-01-01

    Polyhexamethylene biguanide (PHMB), a broad spectrum disinfectant against many pathogens, was used as a stabilizing ligand for the synthesis of fairly uniform silver nanoparticles. The particles formed were characterized using UV-visible spectroscopy, FTIR, dynamic light scattering, electrophoretic mobility, and TEM to measure their morphology and surface chemistry. PHMB-functionalized silver nanoparticles were then evaluated for their antimicrobial activity against a gram-negative bacterial strain, Escherichia coli. These silver nanoparticles were found to have about 100 times higher bacteriostatic and bactericidal activities, compared to the previous reports, due to the combined antibacterial effect of silver nanoparticles and PHMB. In addition to other applications, PHMB-functionalized silver nanoparticles would be extremely useful in textile industry due to the strong interaction of PHMB with cellulose fabrics. PMID:22625664

  9. Polyhexamethylene biguanide functionalized cationic silver nanoparticles for enhanced antimicrobial activity

    NASA Astrophysics Data System (ADS)

    Ashraf, Sumaira; Akhtar, Nasrin; Ghauri, Muhammad Afzal; Rajoka, Muhammad Ibrahim; Khalid, Zafar M.; Hussain, Irshad

    2012-05-01

    Polyhexamethylene biguanide (PHMB), a broad spectrum disinfectant against many pathogens, was used as a stabilizing ligand for the synthesis of fairly uniform silver nanoparticles. The particles formed were characterized using UV-visible spectroscopy, FTIR, dynamic light scattering, electrophoretic mobility, and TEM to measure their morphology and surface chemistry. PHMB-functionalized silver nanoparticles were then evaluated for their antimicrobial activity against a gram-negative bacterial strain, Escherichia coli. These silver nanoparticles were found to have about 100 times higher bacteriostatic and bactericidal activities, compared to the previous reports, due to the combined antibacterial effect of silver nanoparticles and PHMB. In addition to other applications, PHMB-functionalized silver nanoparticles would be extremely useful in textile industry due to the strong interaction of PHMB with cellulose fabrics.

  10. Occupationally derived chemicals in breast milk.

    PubMed

    Wolff, M S

    1983-01-01

    Exogenously derived chemicals have been widely reported in breast milk. Chemicals typically found in occupational exposures, including trace metals, solvents, and halogenated hydrocarbons, are reviewed, in terms of milk partition factors, potential infant exposures, and possible infant health effects. In addition to ingestion of a chemical from breast milk, an infant incurs a neonatal body burden of a chemical due to transplacental migration from maternal blood. For trace metals, neonatal blood levels are similar to maternal blood levels. Partition of metals to milk is less efficient, but nevertheless can contribute significantly to an infant's body burden. For lipid-soluble pesticide residues and halogenated biphenyls, neonatal body burden is much less than that of the mother, but transfer to milk is efficient, due to the high proportion of milk fat. It is suggested that potential organic mercury toxicity can be estimated from concentration in maternal blood or milk. For other chemicals, available data are not sufficient to evaluate short- or long-term health effects. However, for many halogenated hydrocarbons, concentrations in normal human milk would permit infant exposure above guidelines for allowable daily intake set by the World Health organization. PMID:6404163

  11. Occupationally derived chemicals in breast milk

    SciTech Connect

    Wolff, M.S.

    1983-01-01

    Exogenously derived chemicals have been widely reported in breast milk. Chemicals typically found in occupational exposures, including trace metals, solvents, and halogenated hydrocarbons, are reviewed, in terms of milk partition factors, potential infant exposures, and possible infant health effects. In addition to ingestion of a chemical from breast milk, an infant incurs a neonatal body burden of a chemical due to transplacental migration from maternal blood. For trace metals, neonatal blood levels are similar to maternal blood levels. Partition of metals to milk is less efficient, but nevertheless can contribute significantly to an infant's body burden. For lipid-soluble pesticide residues and halogenated biphenyls, neonatal body burden is much less than that of the mother, but transfer to milk is efficient, due to the high proportion of milk fat. It is suggested that potential organic mercury toxicity can be estimated from concentration in maternal blood or milk. For other chemicals, available data are not sufficient to evaluate short- or long-term health effects. However, for many halogenated hydrocarbons, concentrations in normal human milk would permit infant exposure above guidelines for allowable daily intake set by the World Health organization.

  12. In Vitro and In Vivo Modulation of Alternative Splicing by the Biguanide Metformin.

    PubMed

    Laustriat, Delphine; Gide, Jacqueline; Barrault, Laetitia; Chautard, Emilie; Benoit, Clara; Auboeuf, Didier; Boland, Anne; Battail, Christophe; Artiguenave, François; Deleuze, Jean-François; Bénit, Paule; Rustin, Pierre; Franc, Sylvia; Charpentier, Guillaume; Furling, Denis; Bassez, Guillaume; Nissan, Xavier; Martinat, Cécile; Peschanski, Marc; Baghdoyan, Sandrine

    2015-01-01

    Major physiological changes are governed by alternative splicing of RNA, and its misregulation may lead to specific diseases. With the use of a genome-wide approach, we show here that this splicing step can be modified by medication and demonstrate the effects of the biguanide metformin, on alternative splicing. The mechanism of action involves AMPK activation and downregulation of the RBM3 RNA-binding protein. The effects of metformin treatment were tested on myotonic dystrophy type I (DM1), a multisystemic disease considered to be a spliceopathy. We show that this drug promotes a corrective effect on several splicing defects associated with DM1 in derivatives of human embryonic stem cells carrying the causal mutation of DM1 as well as in primary myoblasts derived from patients. The biological effects of metformin were shown to be compatible with typical therapeutic dosages in a clinical investigation involving diabetic patients. The drug appears to act as a modifier of alternative splicing of a subset of genes and may therefore have novel therapeutic potential for many more diseases besides those directly linked to defective alternative splicing. PMID:26528939

  13. Study of epigenetic properties of Poly(HexaMethylene Biguanide) hydrochloride (PHMB).

    PubMed

    Creppy, Edmond E; Diallo, Aboudoulatif; Moukha, Serge; Eklu-Gadegbeku, Christophe; Cros, Daniel

    2014-08-01

    Poly(HexaMethylene Biguanide) hydrochloride (PHMB) CAS No. [32289-58-0] is a particularly effective member of the biguanides antiseptic chemical group, and has been in use since the early fifties in numerous applications. It has been proposed that PHMB be classified as a category 3 carcinogen although PHMB is not genotoxic. It has been hypothesized that PHMB may have epigenetic properties effects, including non-genotoxic modifications of DNA bases, DNA methylation and mitogenic cytokine production. These properties have been assessed in vitro using 3 cell types: Caco-2 cells (from a human colon adenocarcinoma) with a non-functional p53 gene. (∆p53: mut p53), N2-A (Neuro-2A cells, mouse neural cells), the brain being a possible target organ in rodents and HepG2 cells (human hepatocellular carcinoma) with functional p53 gene. From the concentration 1 µg/mL up to 20 µg/mL of PHMB, no effect was observed, either growth stimulation or inhibition. Viability testing using neutral red led to an IC 50 of 20-25 µg/mL after treatment with PHMB for 3 h, whereas the MTT test led to IC50 values of 80 µg/mL, 160 µg/mL and 160 µg/mL respectively for HepG2 cells, Neuro-2A cells and Caco-2 cells. PHMB does not induce significant oxidative stress (production of MDA or lipoperoxidation, nor does it induce hydroxylation of DNA (8-OH-dG) and/or its hypermethylation (m5dC), the latter being strongly implicated in DNA replication and regulation and cell division. PHMB does not induce significant production of mitogenic cytokines such as TNF-α (tumor necrosis factor), interleukins (IL-1 alpha), and the transcription factor nuclear factor kappa B (NF-κB) which can cause either apoptosis or stimulate the growth of transformed cells or tumors. Instead, from concentrations of 20 to 100 µg/mL, PHMB kills cells of all types in less than 3 h. The expression of genes involved in the mechanisms of cell death induced by PHMB, including p53, the pro apoptotic gene bax and others, the anti-apoptotic bcl-2 and caspase-3 has been evaluated by RT-PCR. Finally, the status of GAP-junctions (GJIC) in the presence of PHMB has been determined and appeared to not be significantly affected. Taken together the data show that in vitro PHMB does not exhibit clear and remarkable epigenetic properties except a slight increase of some cytokines and transcription factor at higher concentrations at which cell lysis occurs rapidly. PMID:25111876

  14. Production of Chemical Derivatives from Renewables

    SciTech Connect

    Davison, Brian; Nghiem, John; Donnelly, Mark; Tsai, Shih-Perng; Frye, John; Landucci, Ron; Griffin, Michael

    1996-06-01

    The purpose of this Cooperative Research and Development Agreement (CRADA) between Lockheed Martin Energy Research Corp., (LMER), Argonne National Laboratory (ANL), National Renewable Energy Laboratory (NREL), and Battelle Memorial Institute, operator of Pacific Northwest National Laboratory (PNNL), (collectively referred to as the 'Contractor'), and Applied Carbochemicals, Inc. (Participant) was to scale-up from bench results an economically promising and competitive process for the production of chemical derivatives from biologically produced succinic acid. The products that were under consideration for production from the succinic acid platform included 1,4-butanediol, {gamma}y-butyrolactone, 2-pyrrolidinone and N-methyl pyrrolidinone. Preliminary economic analyses indicated that this platform was competitive with the most recent petrochemical routes. The Contractors and participant are hereinafter jointly referred to as the 'Parties.' Research to date in succinic acid fermentation, separation and genetic engineering resulted in a potentially economical process based on the use of an Escherichia coli strain AFP111 with suitable characteristics for the production of succinic acid from glucose. Economic analysis has shown that higher value commodity chemicals can be economically produced from succinic acid based on preliminary laboratory findings and predicted catalytic parameters. At the time, the current need was to provide the necessary laboratory follow-up information to properly optimize, design and operate a pilot scale process. The purpose of the pilot work was to validate the integrated process, assure 'robustness' of the process, define operating conditions, and provide samples for potential customer evaluation. The data from the pilot scale process was used in design and development of a full scale production facility. A new strain, AFP111 (patented), discovered at ANL was tested and developed for process use at the Oak Ridge National Laboratory (ORNL) and ANL. The operability and product formation are attractive for this strain and effort was being directed at process development and optimization. Key to the transition from the fermentative production unit operation to the chemical catalysis is the 'clean-up' of fermentation broth, succinic acid formation from the salt, and succinic acid concentration. These steps are accomplished by a two-stage membrane ED separation process developed at AWL. Although the current process is well developed, possible modifications and optimization may be called for as development work continues in both the fermentation and catalysis areas. Research to date performed at PNNL has demonstrated that succinic acid can be converted to value added chemicals such as 1,4-butanediol, {gamma}-butyrolactone, N-methyl pyrrolidinone, and 2 pyrrolidinone with high conversion and selectivities. Continued research will be performed in catalyst development and reaction condition optimization to move this work from the bench scale to the pilot scale. All development of the process was guided by the NREL technoeconomic model. The model showed that direct aqueous phase catalysis of succinic acid to 1,4-butanediol, {gamma}-butyrolactone, and N-methyl pyrrolidinone provided significant economical advantages in the market, the margin, and the return on capital investment over existing petrochemical processes for production of these compounds. The model also provided the baseline for evaluating current laboratory research. As data from the bench and pilot work were made available the model was modified and appropriate sensitivities ran to determine impact of the process changes and optimization. The report will present the planned CRADA tasks followed by the results. The results section has an overall project summary follwed by more detailed reports from the participants. This is a nonproprietary report; additional proprietary information may be made available subject to acceptance of the appropriate proprietary information agreements.

  15. Relevance of the OCT1 transporter to the antineoplastic effect of biguanides

    SciTech Connect

    Segal, Eric D.; Yasmeen, Amber; Beauchamp, Marie-Claude; Rosenblatt, Joshua; Segal Cancer Center, Lady Davis Institute of Medical Research, McGill University, Montreal, Quebec ; Pollak, Michael; Department of Oncology, McGill University, Montreal, Quebec ; Gotlieb, Walter H.

    2011-11-04

    Highlights: Black-Right-Pointing-Pointer siRNA knockdown of OCT1 reduced sensitivity of EOC cells to metformin, but not to another biguanide, phenformin. Black-Right-Pointing-Pointer Suppression of OCT1 also affects the activation of AMP kinase in response to metformin, but not to phenformin. Black-Right-Pointing-Pointer Direct actions of metformin may be limited by low OCT1 expression in EOC tumors. Black-Right-Pointing-Pointer Phenformin could be used as an alternative biguanide. -- Abstract: Epidemiologic and laboratory data suggesting that metformin has antineoplastic activity have led to ongoing clinical trials. However, pharmacokinetic issues that may influence metformin activity have not been studied in detail. The organic cation transporter 1 (OCT1) is known to play an important role in cellular uptake of metformin in the liver. We show that siRNA knockdown of OCT1 reduced sensitivity of epithelial ovarian cancer cells to metformin, but interestingly not to another biguanide, phenformin, with respect to both activation of AMP kinase and inhibition of proliferation. We observed that there is heterogeneity between primary human tumors with respect to OCT1 expression. These results suggest that there may be settings where drug uptake limits direct action of metformin on neoplastic cells, raising the possibility that metformin may not be the optimal biguanide for clinical investigation.

  16. Study of Epigenetic Properties of Poly(HexaMethylene Biguanide) Hydrochloride (PHMB)

    PubMed Central

    Creppy, Edmond E.; Diallo, Aboudoulatif; Moukha, Serge; Eklu-Gadegbeku, Christophe; Cros, Daniel

    2014-01-01

    Poly(HexaMethylene Biguanide) hydrochloride (PHMB) CAS No. [32289-58-0] is a particularly effective member of the biguanides antiseptic chemical group, and has been in use since the early fifties in numerous applications. It has been proposed that PHMB be classified as a category 3 carcinogen although PHMB is not genotoxic. It has been hypothesized that PHMB may have epigenetic properties effects, including non-genotoxic modifications of DNA bases, DNA methylation and mitogenic cytokine production. These properties have been assessed in vitro using 3 cell types: Caco-2 cells (from a human colon adenocarcinoma) with a non-functional p53 gene. (∆p53: mut p53), N2-A (Neuro-2A cells, mouse neural cells), the brain being a possible target organ in rodents and HepG2 cells (human hepatocellular carcinoma) with functional p53 gene. From the concentration 1 μg/mL up to 20 μg/mL of PHMB, no effect was observed, either growth stimulation or inhibition. Viability testing using neutral red led to an IC 50 of 20–25 μg/mL after treatment with PHMB for 3 h, whereas the MTT test led to IC50 values of 80 μg/mL, 160 μg/mL and 160 μg/mL respectively for HepG2 cells, Neuro-2A cells and Caco-2 cells. PHMB does not induce significant oxidative stress (production of MDA or lipoperoxidation, nor does it induce hydroxylation of DNA (8-OH-dG) and/or its hypermethylation (m5dC), the latter being strongly implicated in DNA replication and regulation and cell division. PHMB does not induce significant production of mitogenic cytokines such as TNF-α (tumor necrosis factor), interleukins (IL-1 alpha), and the transcription factor nuclear factor kappa B (NF-κB) which can cause either apoptosis or stimulate the growth of transformed cells or tumors. Instead, from concentrations of 20 to 100 μg/mL, PHMB kills cells of all types in less than 3 h. The expression of genes involved in the mechanisms of cell death induced by PHMB, including p53, the pro apoptotic gene bax and others, the anti-apoptotic bcl-2 and caspase-3 has been evaluated by RT-PCR. Finally, the status of GAP-junctions (GJIC) in the presence of PHMB has been determined and appeared to not be significantly affected. Taken together the data show that in vitro PHMB does not exhibit clear and remarkable epigenetic properties except a slight increase of some cytokines and transcription factor at higher concentrations at which cell lysis occurs rapidly. PMID:25111876

  17. Chemical Conversions of Biomass-Derived Platform Chemicals over Copper-Silica Nanocomposite Catalysts.

    PubMed

    Upare, Pravin P; Hwang, Young Kyu; Lee, Jong-Min; Hwang, Dong Won; Chang, Jong-San

    2015-07-20

    Biomass and biomass-derived carbohydrates have a high extent of functionality, unlike petroleum, which has limited functionality. In biorefinery applications, the development of methods to control the extent of functionality in final products intended for use as fuels and chemicals is a challenge. In the chemical industry, heterogeneous catalysis is an important tool for the defunctionalization of functionalized feedstocks and biomass-derived platform chemicals to produce value-added chemicals. Herein, we review the recent progress in this field, mainly of vapor phase chemical conversion of biomass-derived C4 -C6 carboxylic acids and esters using copper-silica nanocomposite catalysts. We also demonstrate that these nanocomposite catalysts very efficiently convert biomass-derived platform chemicals into cyclic compounds, such as lactones and hydrofurans, with high selectivities and yields. PMID:26192888

  18. Chemicals from coal. Utilization of coal-derived phenolic compounds

    SciTech Connect

    Song, C.; Schobert, H.H.

    1999-07-01

    This article provides an overview for possible utilization of coal-derived phenolic compounds. Phenolic compounds are abundant in coal-derived liquids. Coal-derived phenolic compounds include phenol, cresol, catechol, methylcatechol, naphthol, and their derivatives. Liquids from coal liquefaction, pyrolysis, gasification, and carbonization are potential sources of phenolic chemicals, although certain processing and separation are needed. There are opportunities for coal-based phenolic chemicals, because there are existing industrial applications and potential new applications. Currently the petrochemical industry produces phenol in multi-step processes, and new research and development has resulted in a one-step process. Selective methylation of phenol can produce a precursor for aromatic engineering plastics. Catalytic oxidation of phenol has been commercialized recently for catechol production. There are potential new uses of phenol that could replace large-volume multi-step chemical processes that are based on benzene as the starting material. New chemical research on coal and coal-derived liquids can pave the way for their non-fuel uses for making chemicals and materials.

  19. Noninvasive metal contacts in chemically derived graphene devices

    NASA Astrophysics Data System (ADS)

    Sundaram, Ravi S.; Gomez-Navarro, Cristina; Lee, Eduardo J. H.; Burghard, Marko; Kern, Klaus

    2009-11-01

    We study the properties of gold contacts on chemically derived graphene devices by scanning photocurrent microscopy and gate-dependent electrical transport measurements. In the as-fabricated devices, negligible potential barriers are found at the gold/graphene interface, reflecting the noninvasive character of the contacts. Device annealing above 300 °C leads to the formation of potential barriers at the contacts concomitant with metal-induced p-type doping of the sheet as a consequence of the diffusion of gold from the electrodes. The transfer characteristics of the chemically derived graphene devices point toward the suppression of Klein tunneling in this material.

  20. Biological and chemical stability of garlic-derived allicin.

    PubMed

    Fujisawa, Hiroyuki; Suma, Kaoru; Origuchi, Kana; Kumagai, Hitomi; Seki, Taiichiro; Ariga, Toyohiko

    2008-06-11

    This study verifies the instability of garlic ( Allium sativum L.)-derived allyl 2-propenylthiosulfinate (allicin) in various aqueous and ethanolic solutions as well as in vegetable oil through chemical and biological analyses performed simultaneously. Crushed fresh garlic cloves generated antibacterial activity and chemically detectable allicin, a major antibacterial principle, and both declined on a daily basis in aqueous and ethanolic solutions at room temperature, showing biological and chemical half-lives of about 6 and 11 days, respectively. Allicin was more stable in 20% alcohol than in water, but surprisingly unstable in vegetable oil, with an activity half-life 0.8 h, as estimated from its antibacterial activity toward Escherichia coli, and a chemical half-life of 3.1 h, based on chromatographic quantification. In alcoholic and aqueous extracts, the biological half-life of allicin tended to be longer than the chemical one, suggesting the occurrence of bioactive compounds other than allicin in the extracts. PMID:18489116

  1. Revisiting the chemical reactivity indices as the state function derivatives. The role of classical chemical hardness

    SciTech Connect

    Malek, Ali; Balawender, Robert

    2015-02-07

    The chemical reactivity indices as the equilibrium state-function derivatives are revisited. They are obtained in terms of the central moments (fluctuation formulas). To analyze the role of the chemical hardness introduced by Pearson [J. Am. Chem. Soc. 105, 7512 (1983)], the relations between the derivatives up to the third-order and the central moments are obtained. As shown, the chemical hardness and the chemical potential are really the principal indices of the chemical reactivity theory. It is clear from the results presented here that the chemical hardness is not the derivative of the Mulliken chemical potential (this means also not the second derivative of the energy at zero-temperature limit). The conventional quadratic dependence of energy, observed at finite temperature, reduces to linear dependence on the electron number at zero-temperature limit. The chemical hardness plays a double role in the admixture of ionic states to the reference neutral state energy: it determines the amplitude of the admixture and regulates the damping of its thermal factor.

  2. Evaluation of novel lactone derivatives for chemically amplified EUV resists

    NASA Astrophysics Data System (ADS)

    Tanaka, Hiroyasu; Mizusaka, Tetsuhiko; Tanagi, Hiroyuki; Furukawa, Kikuo; Yamamoto, Hiroki; Kozawa, Takahiro

    2015-03-01

    EUV lithography is the most favorable process for high volume manufacturing of semiconductor devices beyond 1X nm half-pitch at present. Many efforts have revealed effective proton sources in acid generation in EUV resists, and the effective proton generation and the control of the generated acid diffusion are required to improve the breakthrough of the resolution ? line width roughness ? sensitivity(RLS) trade-off. To clarify the lithographic performance of these derivatives, we synthesized the acrylic ter/tetrapolymers containing novel lactone derivatives - LCHO and LAATB - as model photopolymers and exposed the resist samples based on these polymers to EUV and EB radiation. On the basis of the lithographic performances of these photoresists, we evaluated the characteristics of lactone derivatives upon exposure to EUV radiation. We discuss the relationship between the chemical structures of these derivatives and lithographic performance.

  3. Biguanide-functionalized mesoporous SBA-15 silica as an efficient solid catalyst for interesterification of vegetable oils.

    PubMed

    Xie, Wenlei; Hu, Libing

    2016-04-15

    The biguanide-functionalized SBA-15 materials were fabricated by grafting of organic biguanide onto the SBA-15 silica through covalent attachments, and then this organic-inorganic hybrid material was employed as solid catalysts for the interesterification of triacylglycerols for the modification of vegetable oils. The prepared catalyst was characterized by FTIR, XRD, SEM, TEM, nitrogen adsorption-desorption and elemental analysis. The biguanide base was successfully tethered onto the SBA-15 silica with no damage to the ordered mesoporous structure of the silica after the organo-functionalization. The solid catalyst had stronger base strength and could catalyze the interesterification of triacylglycerols. The fatty acid compositions and triacylglycerol profiles of the interesterified products were noticeably varied following the interesterification. The reaction parameters, namely substrate ratio, reaction temperature, catalyst loading and reaction time, were investigated for the interesterification of soybean oil with methyl decanoate. The catalyst could be reused for at least four cycles without significant loss of activity. PMID:26616928

  4. The biguanides metformin and phenformin inhibit angiogenesis, local and metastatic growth of breast cancer by targeting both neoplastic and microenvironment cells.

    PubMed

    Orecchioni, Stefania; Reggiani, Francesca; Talarico, Giovanna; Mancuso, Patrizia; Calleri, Angelica; Gregato, Giuliana; Labanca, Valentina; Noonan, Douglas M; Dallaglio, Katiuscia; Albini, Adriana; Bertolini, Francesco

    2015-03-15

    The human white adipose tissue (WAT) contains progenitors with cooperative roles in breast cancer (BC) angiogenesis, local and metastatic progression. The biguanide Metformin (Met), commonly used for Type 2 diabetes, might have activity against BC and was found to inhibit angiogenesis in vivo. We studied Met and another biguanide, phenformin (Phe), in vitro and in vivo in BC models. In vitro, biguanides activated AMPK, inhibited Complex 1 of the respiratory chain and induced apoptosis of BC and WAT endothelial cells. In coculture, biguanides inhibited the production of several angiogenic proteins. In vivo, biguanides inhibited local and metastatic growth of triple negative and HER2+ BC in immune-competent and immune-deficient mice orthotopically injected with BC. Biguanides inhibited local and metastatic BC growth in a genetically engineered murine model model of HER2+ BC. In vivo, biguanides increased pimonidazole binding (but not HIF-1 expression) of WAT progenitors, reduced tumor microvessel density and altered the vascular pericyte/endothelial cell ratio, so that cancer vessels displayed a dysplastic phenotype. Phe was significantly more active than Met both in vitro and in vivo. Considering their safety profile, biguanides deserve to be further investigated for BC prevention in high-risk subjects, in combination with chemo and/or targeted therapy and/or as post-therapy consolidation or maintenance therapy for the prevention of BC recurrence. PMID:25196138

  5. Metabolic determinants of cancer cell sensitivity to glucose limitation and biguanides

    NASA Astrophysics Data System (ADS)

    Birsoy, Kıvanç; Possemato, Richard; Lorbeer, Franziska K.; Bayraktar, Erol C.; Thiru, Prathapan; Yucel, Burcu; Wang, Tim; Chen, Walter W.; Clish, Clary B.; Sabatini, David M.

    2014-04-01

    As the concentrations of highly consumed nutrients, particularly glucose, are generally lower in tumours than in normal tissues, cancer cells must adapt their metabolism to the tumour microenvironment. A better understanding of these adaptations might reveal cancer cell liabilities that can be exploited for therapeutic benefit. Here we developed a continuous-flow culture apparatus (Nutrostat) for maintaining proliferating cells in low-nutrient media for long periods of time, and used it to undertake competitive proliferation assays on a pooled collection of barcoded cancer cell lines cultured in low-glucose conditions. Sensitivity to low glucose varies amongst cell lines, and an RNA interference (RNAi) screen pinpointed mitochondrial oxidative phosphorylation (OXPHOS) as the major pathway required for optimal proliferation in low glucose. We found that cell lines most sensitive to low glucose are defective in the OXPHOS upregulation that is normally caused by glucose limitation as a result of either mitochondrial DNA (mtDNA) mutations in complex I genes or impaired glucose utilization. These defects predict sensitivity to biguanides, antidiabetic drugs that inhibit OXPHOS, when cancer cells are grown in low glucose or as tumour xenografts. Notably, the biguanide sensitivity of cancer cells with mtDNA mutations was reversed by ectopic expression of yeast NDI1, a ubiquinone oxidoreductase that allows bypass of complex I function. Thus, we conclude that mtDNA mutations and impaired glucose utilization are potential biomarkers for identifying tumours with increased sensitivity to OXPHOS inhibitors.

  6. Metabolic determinants of cancer cell sensitivity to glucose limitation and biguanides

    PubMed Central

    Birsoy, K?van; Possemato, Richard; Lorbeer, Franziska K.; Bayraktar, Erol C.; Thiru, Prathapan; Yucel, Burcu; Wang, Tim; Chen, Walter W.; Clish, Clary B.; Sabatini, David M.

    2014-01-01

    As the concentrations of highly consumed nutrients, particularly glucose, are generally lower in tumours than in normal tissues1,2, cancer cells must adapt their metabolism to the tumour microenvironment. A better understanding of these adaptations might reveal cancer cell liabilities that can be exploited for therapeutic benefit. Here, we developed a continuous flow culture apparatus (Nutrostat) for maintaining proliferating cells in low nutrient media for long periods of time and used it to undertake competitive proliferation assays on a pooled collection of barcoded cancer cell lines cultured in low glucose conditions. Sensitivity to low glucose varies amongst cell lines, and an RNAi screen pinpointed mitochondrial oxidative phosphorylation (OXPHOS) as the major pathway required for optimal proliferation in low glucose. We found that cell lines most sensitive to low glucose are defective in the upregulation of OXPHOS normally caused by glucose limitation as a result of either mtDNA mutations in Complex I genes or impaired glucose utilization. These defects predict sensitivity to biguanides, anti-diabetic drugs that inhibit OXPHOS3,4, when cancer cells are grown in low glucose or as tumour xenografts. Remarkably, the biguanide sensitivity of cancer cells with mtDNA mutations was reversed by ectopic expression of yeast NDI1, a ubiquinone oxidoreductase that allows bypass of Complex I function5. Thus, we conclude that mtDNA mutations and impaired glucose utilization are potential biomarkers for identifying tumours with increased sensitivity to OXPHOS inhibitors. PMID:24670634

  7. Analytical Derivation of Moment Equations in Stochastic Chemical Kinetics

    PubMed Central

    Sotiropoulos, Vassilios; Kaznessis, Yiannis N.

    2011-01-01

    The master probability equation captures the dynamic behavior of a variety of stochastic phenomena that can be modeled as Markov processes. Analytical solutions to the master equation are hard to come by though because they require the enumeration of all possible states and the determination of the transition probabilities between any two states. These two tasks quickly become intractable for all but the simplest of systems. Instead of determining how the probability distribution changes in time, we can express the master probability distribution as a function of its moments, and, we can then write transient equations for the probability distribution moments. In 1949, Moyal defined the derivative, or jump, moments of the master probability distribution. These are measures of the rate of change in the probability distribution moment values, i.e. what the impact is of any given transition between states on the moment values. In this paper we present a general scheme for deriving analytical moment equations for any N-dimensional Markov process as a function of the jump moments. Importantly, we propose a scheme to derive analytical expressions for the jump moments for any N-dimensional Markov process. To better illustrate the concepts, we focus on stochastic chemical kinetics models for which we derive analytical relations for jump moments of arbitrary order. Chemical kinetics models are widely used to capture the dynamic behavior of biological systems. The elements in the jump moment expressions are a function of the stoichiometric matrix and the reaction propensities, i.e the probabilistic reaction rates. We use two toy examples, a linear and a non-linear set of reactions, to demonstrate the applicability and limitations of the scheme. Finally, we provide an estimate on the minimum number of moments necessary to obtain statistical significant data that would uniquely determine the dynamics of the underlying stochastic chemical kinetic system. The first two moments only provide limited information, especially when complex, non-linear dynamics are involved. PMID:21949443

  8. Marine derived polysaccharides for biomedical applications: chemical modification approaches.

    PubMed

    d'Ayala, Giovanna Gomez; Malinconico, Mario; Laurienzo, Paola

    2008-01-01

    Polysaccharide-based biomaterials are an emerging class in several biomedical fields such as tissue regeneration, particularly for cartilage, drug delivery devices and gelentrapment systems for the immobilization of cells. Important properties of the polysaccharides include controllable biological activity, biodegradability, and their ability to form hydrogels. Most of the polysaccharides used derive from natural sources; particularly, alginate and chitin, two polysaccharides which have an extensive history of use in medicine, pharmacy and basic sciences, and can be easily extracted from marine plants (algae kelp) and crab shells, respectively. The recent rediscovery of poly-saccharidebased materials is also attributable to new synthetic routes for their chemical modification, with the aim of promoting new biological activities and/or to modify the final properties of the biomaterials for specific purposes. These synthetic strategies also involve the combination of polysaccharides with other polymers. A review of the more recent research in the field of chemical modification of alginate, chitin and its derivative chitosan is presented. Moreover, we report as case studies the results of our recent work concerning various different approaches and applications of polysaccharide-based biomaterials, such as the realization of novel composites based on calcium sulphate blended with alginate and with a chemically modified chitosan, the synthesis of novel alginate-poly(ethylene glycol) copolymers and the development of a family of materials based on alginate and acrylic polymers of potential interest as drug delivery systems. PMID:18830142

  9. Deriving uncertainty factors for threshold chemical contaminants in drinking water.

    PubMed

    Ritter, Leonard; Totman, Céline; Krishnan, Kannan; Carrier, Richard; Vézina, Anne; Morisset, Véronique

    2007-10-01

    Uncertainty factors are used in the development of drinking-water guidelines to account for uncertainties in the database, including extrapolations of toxicity from animal studies and variability within humans, which result in some uncertainty about risk. The application of uncertainty factors is entrenched in toxicological risk assessment worldwide, but is not applied consistently. This report, prepared in collaboration with Health Canada, provides an assessment of the derivation of the uncertainty factor assumptions used in developing drinking-water quality guidelines for chemical contaminants. Assumptions used by Health Canada in the development of guidelines were compared to several other major regulatory jurisdictions. This assessment has revealed that uncertainty factor assumptions have been substantially influenced by historical practice. While the application of specific uncertainty factors appears to be well entrenched in regulatory practice, a well-documented and disciplined basis for the selection of these factors was not apparent in any of the literature supporting the default assumptions of Canada, the United States, Australia, or the World Health Organization. While there is a basic scheme used in most cases in developing drinking-water quality guidelines for nonthreshold contaminants by the jurisdictions included in this report, additional factors are sometimes included to account for other areas of uncertainty. These factors may include extrapolating subchronic data to anticipated chronic exposure, or use of a LOAEL instead of a NOAEL. The default value attributed to each uncertainty factor is generally a factor of 3 or 10; however, again, no comprehensive guidance to develop and apply these additional uncertainty factors was evident from the literature reviewed. A decision tree has been developed to provide guidance for selection of appropriate uncertainty factors, to account for the range of uncertainty encountered in the risk assessment process. Recent development of a series of "decision trees" by WHO to derive chemical specific adjustment factors for inter- and intraspecies variability may present an opportunity for a more systematic approach for the identification of evidence-based uncertainty factors. PMID:17934949

  10. Physico-chemical characterization of sesame oil derivatives.

    PubMed

    Zanardi, Iacopo; Travagli, Valter; Gabbrielli, Alessandro; Chiasserini, Luisa; Bocci, Velio

    2008-09-01

    Ozone treatment of commercially available vegetable oils gives rise to the formation of chemical species that are responsible for the therapeutic properties of ozonated oil derivatives in dermatological diseases. In the last years, these products have been successfully used as a topical disinfectant in a number of serious skin affections. The medical application of empirically prepared ozonated oil has yielded striking improvements with unexpected and rapid healing, compelling us to begin a long-range study aiming first to define the main characteristics of the most common ozonated vegetable oils, about which there is usually no medical consensus because of the lack of standardization of their technological parameters. Sesame oil was selected because of its great amount of polyunsaturated acyl groups, as well as natural antioxidants. Moreover, we have determined the kinetics and optimal conditions of ozonation (e.g., ozone concentrations, time of exposure, temperature) for obtaining an ozonated oil characterized by well-established technological and physico-chemical properties, namely an accurate peroxide value determination. On the basis of the results, we have gained an understanding of the modifications of the vegetable oils during the ozonation process. PMID:18679737

  11. Unique marine derived cyanobacterial biosynthetic genes for chemical diversity.

    PubMed

    Kleigrewe, Karin; Gerwick, Lena; Sherman, David H; Gerwick, William H

    2016-02-01

    Covering: 2010 to July 2015. Previous review: Nat. Prod. Rep., 2010, 27, 1048-1065Cyanobacteria are a prolific source of structurally unique and biologically active natural products that derive from intriguing biochemical pathways. Advancements in genome sequencing have accelerated the identification of unique modular biosynthetic gene clusters in cyanobacteria and reveal a wealth of unusual enzymatic reactions involved in their construction. This article examines several interesting mechanistic transformations involved in cyanobacterial secondary metabolite biosynthesis with a particular focus on marine derived modular polyketide synthases (PKS), nonribosomal peptide synthetases (NRPS) and combinations thereof to form hybrid natural products. Further, we focus on the cyanobacterial genus Moorea and the co-evolution of its enzyme cassettes that create metabolic diversity. Progress in the development of heterologous expression systems for cyanobacterial gene clusters along with chemoenzymatic synthesis makes it possible to create new analogs. Additionally, phylum-wide genome sequencing projects have enhanced the discovery rate of new natural products and their distinctive enzymatic reactions. Summarizing, cyanobacterial biosynthetic gene clusters encode for a large toolbox of novel enzymes that catalyze unique chemical reactions, some of which may be useful in synthetic biology. PMID:26758451

  12. Physical and chemical characterization of waste wood derived biochars.

    PubMed

    Yargicoglu, Erin N; Sadasivam, Bala Yamini; Reddy, Krishna R; Spokas, Kurt

    2015-02-01

    Biochar, a solid byproduct generated during waste biomass pyrolysis or gasification in the absence (or near-absence) of oxygen, has recently garnered interest for both agricultural and environmental management purposes owing to its unique physicochemical properties. Favorable properties of biochar include its high surface area and porosity, and ability to adsorb a variety of compounds, including nutrients, organic contaminants, and some gases. Physical and chemical properties of biochars are dictated by the feedstock and production processes (pyrolysis or gasification temperature, conversion technology and pre- and post-treatment processes, if any), which vary widely across commercially produced biochars. In this study, several commercially available biochars derived from waste wood are characterized for physical and chemical properties that can signify their relevant environmental applications. Parameters characterized include: physical properties (particle size distribution, specific gravity, density, porosity, surface area), hydraulic properties (hydraulic conductivity and water holding capacity), and chemical and electrochemical properties (organic matter and organic carbon contents, pH, oxidation-reduction potential and electrical conductivity, zeta potential, carbon, nitrogen and hydrogen (CHN) elemental composition, polycyclic aromatic hydrocarbons (PAHs), heavy metals, and leachable PAHs and heavy metals). A wide range of fixed carbon (0-47.8%), volatile matter (28-74.1%), and ash contents (1.5-65.7%) were observed among tested biochars. A high variability in surface area (0.1-155.1g/m(2)) and PAH and heavy metal contents of the solid phase among commercially available biochars was also observed (0.7-83 mg kg(-1)), underscoring the importance of pre-screening biochars prior to application. Production conditions appear to dictate PAH content--with the highest PAHs observed in biochar produced via fast pyrolysis and lowest among the gasification-produced biochars. PMID:25464942

  13. Antimicrobial electrospun membranes of chitosan/poly(ethylene oxide) incorporating poly(hexamethylene biguanide) hydrochloride.

    PubMed

    Dilamian, M; Montazer, M; Masoumi, J

    2013-04-15

    Here, antimicrobial nanofibrous membranes were produced by electrospinning of chitosan/poly(ethylene oxide) (PEO) solution in the presence of poly(hexamethylene biguanide) hydrochloride (PHMB). The influence of PHMB on the electrospinnability and antimicrobial properties of chitosan/PEO nanofibers were studied. Further, viscosity of the solutions as well as morphology of the nanofibrous structures were investigated. Results revealed that incorporation of PHMB in chitosan/PEO solutions led to decrease in the zero-shear rate viscosity up to 20%. Moreover, increasing PHMB from 0.5 mM to 1 mM led to formation of thinner fibers with diameters ranging from 240 nm to 60 nm, respectively. Fourier transform infrared (FT-IR) spectrums indicated the functional groups of chitosan, PEO and PHMB in nanofibrous structure. Differential scanning calorimetry (DSC) thermograms indicated interaction of PHMB with PEO and chitosan through alteration in the thermal behavior of the nanofibers. Inhibition of the bacteria growth for both Escherichia coli and Staphylococcus aureus were achieved on the PHMB loaded nanofibers. Also, a burst release of PHMB from mats has been observed in the first hour. These findings suggest that there is a great potential in fabrication of biomaterials with incorporation of PHMB using electrospinning. PMID:23544550

  14. Effects of Polyhexamethylene Biguanide and Polyquaternium-1 on Phospholipid Bilayer Structure and Dynamics.

    PubMed

    Horner, Ian J; Kraut, Nadine D; Hurst, Jerod J; Rook, Alyssa M; Collado, Crystal M; Atilla-Gokcumen, G Ekin; Maziarz, E Peter; Liu, X Michael; Merchea, Mohinder M; Bright, Frank V

    2015-08-20

    Multipurpose solutions (MPS) are a single solution that functions to simultaneously rinse, disinfect, clean, and store soft contact lenses. Several commercial MPS products contain polyhexamethylene biguanide (PHMB) and/or polyquaternium-1 (PQ-1) as antimicrobial agents. In this paper we have created an in vitro small unilamellar vesicle (SUV) model of the corneal epithelial surface, and we have assessed the interactions of PHMB and PQ-1 with several model biomembranes by using fluorescence spectroscopy, dynamic light scattering (DLS), and liquid chromatography-mass spectrometry (LC-MS). Steady-state and time-resolved fluorescence were used to assess the membrane acyl chain and polar headgroup region local microenvironment as a function of added PHMB or PQ-1. DLS was used to detect and quantify SUV aggregation induced by PHMB and PQ-1. LC-MS was used to determine the liposomal composition from any precipitated materials in comparison to the as-prepared SUVs. The results are consistent with PHMB adsorbing onto and PQ-1 intercalating into the biomembrane structure. The differences between the two interaction mechanisms have substantial impacts on the biomembrane dynamics and stability. PMID:26239890

  15. Mucoadhesive system formed by liquid crystals for buccal administration of poly(hexamethylene biguanide) hydrochloride.

    PubMed

    Souza, Carla; Watanabe, Evandro; Borgheti-Cardoso, Livia Neves; De Abreu Fantini, Márcia Carvalho; Lara, Marilisa Guimarães

    2014-12-01

    Antimicrobial approaches are valuable in controlling the development of buccal diseases, but some antibacterial agents have a short duration of activity. Therefore, the development of prolonged delivery systems would be advantageous. Liquid crystalline systems comprising monoolein (GMO)/water have been considered to be a potential vehicle to deliver drugs to the buccal mucosa because of the phase properties that allow for controlled drug release as well as its mucoadhesive properties. Therefore, the aim of this study was to develop a GMO/water system for the slow release of poly(hexamethylene biguanide) hydrochloride (PHMB) on the buccal mucosa and test the properties of this system with regard to swelling, release profile, antimicrobial activity, and strength of mucoadhesion, with the overall goal of treating buccal infections. The tested systems were capable of modulating drug release, which is controlled by diffusion of the drug throughout the system. Furthermore, PHMB appeared to improve the mucoadhesive properties of the system and may synergistically act with the drug to promote antimicrobial activity against S. mutas and C. albicans, indicating that liquid crystals may be suitable for the administration of PHMB on the buccal mucosa. Therefore, this system could be proposed as a novel system for mucoadhesive drug delivery. PMID:25336429

  16. The Evaluation of Polyhexamethylene Biguanide (PHMB) as a Disinfectant for Adenovirus

    PubMed Central

    Romanowski, Eric G.; Yates, Kathleen A.; O’Connor, Katherine E.; Mah, Francis S.; Shanks, Robert M. Q.; Kowalski, Regis P.

    2013-01-01

    Purpose Swimming pools can be a vector for transmission of adenovirus ocular infections. Polyhexamethylene biguanide (PHMB) is a disinfectant used in swimming pools and hot tubs. The current study determined whether PHMB is an effective disinfectant against ocular adenovirus serotypes at a concentration used to disinfect swimming pools and hot tubs. Methods The direct disinfecting activity of PHMB was determined in triplicate assays by incubating nine human adenovirus types (1, 2, 3, 4, 5, 7a, 8, 19, and 37) with 50 and 0 PPM (µg/ml) of PHMB for 24 hours at room temperature, to simulate swimming pool temperatures, or 40°C, to simulate hot tub temperatures. Plaque assays determined adenovirus titers after incubation. Titers were Log10 converted and mean ± standard deviation Log10 reductions from controls were calculated. Virucidal (greater than 99.9%) decreases in mean adenovirus titers after PHMB treatment were determined for each adenovirus type and temperature tested. Results At room temperature, 50 PPM of PHMB produced mean reductions in titers less than 1 Log10 for all adenovirus types tested. At 40°C, 50 PPM of PHMB produced mean reductions in titers less than 1 Log10 for two adenovirus types and greater than 1 Log10, but less than 3 Log10, for seven of nine adenovirus types. Conclusions 50 PPM of PHMB was not virucidal against adenovirus at temperatures consistent with swimming pools or hot tubs. Clinical Relevance Recreational water maintained and sanitized with PHMB has the potential to serve as a vector for the transmission of ocular adenovirus infections. PMID:23450376

  17. Iodine derivatives of chemically modified gum Arabic microspheres.

    PubMed

    Ganie, Showkat A; Ali, Akbar; Mazumdar, Nasreen

    2015-09-20

    Acetylated gum Arabic (AGA) derivatives with different degrees of substitution (DS 0.97-2.74) were synthesized using acetyl chloride and a base under varying reaction conditions. The AGA derivatives were obtained in the form of microspheres and thereafter stable iodine products were prepared by doping the microspheres with an iodinating agent, iodine monochloride (ICl). The reaction between electrophilic iodine and polar carbonyl groups was studied by FT-IR, (1)H-NMR, and UV-VIS spectroscopies. The products were also characterized by DSC, TGA and SEM studies. The incorporated iodine was released in aqueous medium as iodide ions (I(-)). A reaction scheme has been proposed for the iodination and de-iodination of the gum derivatives. This work suggests that the iodine derivatives of modified gum Arabic could be used as a source of iodide ions which is the nutritional form of iodine. PMID:26050909

  18. Coumarin heterocyclic derivatives: chemical synthesis and biological activity.

    PubMed

    Medina, Fernanda G; Marrero, Joaquín G; Macías-Alonso, Mariana; González, Magdalena C; Córdova-Guerrero, Iván; Teissier García, Ariana G; Osegueda-Robles, Soraya

    2015-09-23

    This review highlights the broad range of science that has arisen from the synthesis of coumarin-linked and fused heterocycle derivatives. Specific topics include their synthesis and biological activity. PMID:26151411

  19. Structural evolution during the reduction of chemically derived graphene oxide

    NASA Astrophysics Data System (ADS)

    Bagri, Akbar; Mattevi, Cecilia; Acik, Muge; Chabal, Yves J.; Chhowalla, Manish; Shenoy, Vivek B.

    2010-07-01

    The excellent electrical, optical and mechanical properties of graphene have driven the search to find methods for its large-scale production, but established procedures (such as mechanical exfoliation or chemical vapour deposition) are not ideal for the manufacture of processable graphene sheets. An alternative method is the reduction of graphene oxide, a material that shares the same atomically thin structural framework as graphene, but bears oxygen-containing functional groups. Here we use molecular dynamics simulations to study the atomistic structure of progressively reduced graphene oxide. The chemical changes of oxygen-containing functional groups on the annealing of graphene oxide are elucidated and the simulations reveal the formation of highly stable carbonyl and ether groups that hinder its complete reduction to graphene. The calculations are supported by infrared and X-ray photoelectron spectroscopy measurements. Finally, more effective reduction treatments to improve the reduction of graphene oxide are proposed.

  20. Microbial production of fatty acid-derived fuels and chemicals

    PubMed Central

    Lennen, Rebecca M; Pfleger, Brian F

    2013-01-01

    Fatty acid metabolism is an attractive route to produce liquid transportation fuels and commodity oleochemicals from renewable feedstocks. Recently, genes and enzymes, which comprise metabolic pathways for producing fatty acid-derived compounds (e.g. esters, alkanes, olefins, ketones, alcohols, polyesters) have been elucidated and used in engineered microbial hosts. The resulting strains often generate products at low percentages of maximum theoretical yields, leaving significant room for metabolic engineering. Economically viable processes will require strains to approach theoretical yields, particularly for replacement of petroleum-derived fuels. This review will describe recent progress toward this goal, highlighting the scientific discoveries of each pathway, ongoing biochemical studies to understand each enzyme, and metabolic engineering strategies that are being used to improve strain performance. PMID:23541503

  1. Chemical applications of neural networks: aromaticity of pyrimidine derivatives.

    PubMed

    Alonso, Mercedes; Miranda, Carlos; Martín, Nazario; Herradón, Bernardo

    2011-12-14

    Neural networks are computational tools able to apprehend non-linear relationships between different parameters, having the capacity to order a large amount of input data and transform them into a graphical pattern of output data. We have previously reported their use for the quantification of the aromaticity through the Euclidean distance between neurons. In this article, we apply the method to a variety of pyrimidine derivatives with electron-donor and electron-withdrawing groups as substituents, with capacity to produce push-pull compounds. We have calculated the aromaticity of benzene (as a reference molecule), parent pyrimidine and other 11 pyrimidine derivatives having amino, dimethylamino and tricyanovinyl substitution. The neural network has been generated using ASE, Λ, NICS(zz)(1) and HOMA as aromaticity descriptors, since our previous work showed that the combination of these indices provided the best performance of the network. On studying the influence of the substituent on the aromaticity of the molecule, we have found that, opposite to benzene derivatives, all the substituents decrease the aromaticity of the ring. The interplay between aromaticity, planarity and push-pull properties of all the substituted pyrimidines has also been addressed. An interesting feature of the neural network to quantify aromaticity is that the importance of the reference reaction used to evaluate energy stabilization and magnetic susceptibility exaltation is minimized. PMID:21879068

  2. Polo and Aurora kinases: lessons derived from chemical biology.

    PubMed

    Taylor, Stephen; Peters, Jan-Michael

    2008-02-01

    During the cell division cycle, mitotic entry, spindle assembly, chromosome segregation, and cytokinesis must all be carefully coordinated to ensure that the two daughter cells inherit all the genetic material required for further growth and development. Central to this coordination are several protein kinases including Aurora A, Aurora B, and the Polo-like kinase, Plk1. A number of small-molecule Aurora and Plk1 inhibitors have been developed because these kinases are seen as attractive anticancer drug targets. These inhibitors are now being widely used as chemical biology tools to understand how these kinases ensure faithful genome transmission. PMID:18249108

  3. Conical intersection seams in polyenes derived from their chemical composition

    SciTech Connect

    Nenov, Artur; Vivie-Riedle, Regina de

    2012-08-21

    The knowledge of conical intersection seams is important to predict and explain the outcome of ultrafast reactions in photochemistry and photobiology. They define the energetic low-lying reachable regions that allow for the ultrafast non-radiative transitions. In complex molecules it is not straightforward to locate them. We present a systematic approach to predict conical intersection seams in multifunctionalized polyenes and their sensitivity to substituent effects. Included are seams that facilitate the photoreaction of interest as well as seams that open competing loss channels. The method is based on the extended two-electron two-orbital method [A. Nenov and R. de Vivie-Riedle, J. Chem. Phys. 135, 034304 (2011)]. It allows to extract the low-lying regions for non-radiative transitions, which are then divided into small linear segments. Rules of thumb are introduced to find the support points for these segments, which are then used in a linear interpolation scheme for a first estimation of the intersection seams. Quantum chemical optimization of the linear interpolated structures yields the final energetic position. We demonstrate our method for the example of the electrocyclic isomerization of trifluoromethyl-pyrrolylfulgide.

  4. Chemical modification of arglabin and biological activity of its new derivatives.

    PubMed

    Adekenov, S M

    2016-04-01

    This review summarizes the results of own research on chemical modification of the molecule of sesquiterpene lactone arglabin from Artemisia glabella Kar. et Kir. Over 70 new arglabin derivatives were obtained which are polyfunctional compounds with oxy functions, atoms of haloids, phosphorus, nitrogen, and cyclopropane fragments. For the first time the results of bioscreening of new arglabin derivatives are reported. PMID:26625839

  5. Chemical equilibrium. [maximizing entropy of gas system to derive relations between thermodynamic variables

    NASA Technical Reports Server (NTRS)

    1976-01-01

    The entropy of a gas system with the number of particles subject to external control is maximized to derive relations between the thermodynamic variables that obtain at equilibrium. These relations are described in terms of the chemical potential, defined as equivalent partial derivatives of entropy, energy, enthalpy, free energy, or free enthalpy. At equilibrium, the change in total chemical potential must vanish. This fact is used to derive the equilibrium constants for chemical reactions in terms of the partition functions of the species involved in the reaction. Thus the equilibrium constants can be determined accurately, just as other thermodynamic properties, from a knowledge of the energy levels and degeneracies for the gas species involved. These equilibrium constants permit one to calculate the equilibrium concentrations or partial pressures of chemically reacting species that occur in gas mixtures at any given condition of pressure and temperature or volume and temperature.

  6. Biorefineries for the production of top building block chemicals and their derivatives.

    PubMed

    Choi, Sol; Song, Chan Woo; Shin, Jae Ho; Lee, Sang Yup

    2015-03-01

    Due to the growing concerns on the climate change and sustainability on petrochemical resources, DOE selected and announced the bio-based top 12 building blocks and discussed the needs for developing biorefinery technologies to replace the current petroleum based industry in 2004. Over the last 10 years after its announcement, many studies have been performed for the development of efficient technologies for the bio-based production of these chemicals and derivatives. Now, ten chemicals among these top 12 chemicals, excluding the l-aspartic acid and 3-hydroxybutyrolactone, have already been commercialized or are close to commercialization. In this paper, we review the current status of biorefinery development for the production of these platform chemicals and their derivatives. In addition, current technological advances on industrial strain development for the production of platform chemicals using micro-organisms will be covered in detail with case studies on succinic acid and 3-hydroxypropionic acid as examples. PMID:25576747

  7. Prediction of blood-brain barrier permeation using quantum chemically derived information.

    PubMed

    Hutter, Michael C

    2003-07-01

    A model for the prediction of the blood-brain distribution (logBB) is obtained by multiple regression analysis of molecular descriptors for a training set of 90 compounds. The majority of the descriptors are derived from quantum chemical information using semi-empirical AM1 calculations to compute fundamental properties of the molecules investigated. The polar surface area of the compounds can be described appropriately by six descriptors derived from the molecular electrostatic potential. This set shows a strong correlation with the observed logBB. Additional quantum chemically computed properties that contribute to the final model comprise the ionization potential and the covalent hydrogen-bond basicity. Complementary descriptors account for the presence of certain chemical groups, the number of hydrogen-bond donors, and the number of rotatable bonds of the compounds. The quality of the fit is further improved by including variables derived from principal component analysis of the molecular geometry. PMID:14677638

  8. Deriving chemical trends from thermal infrared spectra of weathered basalt: Implications for remotely determining chemical trends on Mars

    NASA Astrophysics Data System (ADS)

    Rampe, Elizabeth B.; Kraft, Michael D.; Sharp, Thomas G.

    2013-07-01

    Variations in chemical composition over a planetary surface can be used to study petrologic and aqueous alteration processes. The desire for such data on Mars has prompted investigators to derive chemistry from models of Thermal Emission Spectrometer data. Although chemistry derived from thermal infrared spectral models is reportedly reliable for unaltered igneous rocks, the martian surface has experienced chemical weathering, which can adversely affect models. Here, we examine weathered basalts from Baynton, Australia, for which chemical weathering trends have been previously characterized, to test how well chemistry and chemical trends can be determined from TIR spectra of weathered rocks. The mineralogy of variably weathered rocks was derived from TIR spectra by linear mixing, and major-element chemistry was calculated from those mineral models. Derived chemistries and trends were compared to those measured by X-ray fluorescence. TIR spectroscopy is sensitive to weathering products in weathering rinds because the products are present in a coating geometry, making it a useful technique for remotely detecting weathered surfaces on planetary surfaces such as Mars. This sensitivity results in significant modeled abundances of weathering products (>80% of all phases) from TIR spectra of weathered Baynton surfaces, despite evidence from microscopy and X-ray diffraction showing that igneous minerals dominate the weathering rind. Measured chemical weathering trends show loss of MgO, CaO, Na2O, and K2O and relative enrichment in Al2O3 and FeOT. The modeled trends are similar to the measured trends, but a closer look at the modeled oxide abundances demonstrates that most oxides (i.e., alkalis, SiO2, and FeOT) are not well modeled, especially for weathered surfaces. The reasons for this are: (1) non-linear mixing and the presence of secondary coatings causes the overestimation of secondary phases in spectral models, and (2) spectral libraries generally lack poorly crystalline and amorphous secondary phases that are common in weathering rinds so that crystalline phases such as phyllosilicates are selected. The martian surface has likely been weathered less pervasively than the Baynton rocks and, therefore, weathering products may be dominated by poorly crystalline and amorphous phases, rather than crystalline phyllosilicates. Adding these phases to spectral libraries could improve bulk chemistry derived from the martian surface; however, if the secondary phases are present in a coating geometry, the derived chemistry will reflect the composition of the coating, and it may be difficult to infer the chemistry of the parent rock.

  9. [Mechanisms of the inhibitive action of 1,4-dihydroisonicotinic acid derivatives in chemical mutagenesis].

    PubMed

    Kuzhir, T D; Goncharova, R I

    1995-01-01

    1.4-Dihydroisonicotinic acid derivatives were used as an example to examine the mechanisms of action of exogenous antimutagens in chemical mutagenesis in eukaryotic organisms. The chemical mutagenesis was stimulated by alkylating agents, mutagens of direct action. The behaviour of alkylating mutagenesis was analysed, which gives an insight into the stages at which antimutagens may be involved in this process. Chemical mutagenesis was demonstrated to be suppressed due to lower molecular doses of the mutagen and by affecting the mechanisms of implementation of chemically induced mutations. Great emphasis was laid on the mechanisms of action of mutagens mediated by the intracellular antimutagenic and reparative systems. A special role is played by the analysis of exogenous antimutagens affecting DNA reparation as the most important step in the process of conversion of primary damages to fixed mutations. The paper presents a review of literature on basic problems of chemical mutagenesis modification. PMID:7767113

  10. Considerations in the Derivation of Water Quality Criteria for Endocrine-disrupting Chemicals

    EPA Science Inventory

    When the USEPA’s 1985 guidelines for deriving numerical water quality criteria (WQC) for the protection of aquatic life were developed there was little anticipation that endocrine-disrupting chemicals (EDCs) would be come a widespread environmental issue. While the basic guidelin...

  11. Gram-positive bacteria as biocatalysts to convert biomass derived sugars into biofuel and chemicals

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The microbial fermentation of biomass derived sugar mixtures is one of the barriers to the overall economic conversion process from lignocellulosic biomass to fuels and chemicals. Although the supply and characteristics of feedstocks vary, biomass hydrolysates usually contain mixed sugars, organic ...

  12. Correlation between chemical structure and rodent repellency of benzoic acid derivatives

    USGS Publications Warehouse

    Fearn, J.E.; DeWitt, J.B.

    1965-01-01

    Sixty-five benzoic acid derivatives were either prepared or obtained from commercial concerns, tested for rat repellency, and their indices of repellency computed. The data from these tests were considered analytically for any correlation between chemical structure and rat repellency. The results suggest a qualitative relationship which is useful in deciding probability of repellency in other compounds.

  13. Identification of a thienopyrimidine derivatives target by a kinome and chemical biology approach.

    PubMed

    Lee, Chulho; Yang, Jee Sun; Han, Gyoonhee

    2015-09-01

    Target identification through chemical biology has been considered one of the most efficient approaches for drug discovery. Thienopyrimidine derivatives were designed to discover potent IκB kinase β (IKKβ) inhibitors based on a known IKKβ inhibitor library. Most of the thienopyrimidine derivatives inhibited nitric oxide and tumor necrosis factor alpha, which are downstream of the NF-κB signaling pathway, but not IKKβ. To identify the appropriate targets of thienopyrimidine analogues, chemical biology approaches, including text mining and a subsequent kinase panel assay from the kinome profiling were used. Based on the results, Fms-like tyrosine kinase 3 was found to be the target for thienopyrimidine derivatives, and was confirmed to be a potent inhibitor for acute myeloid leukemia. PMID:26186885

  14. Production of Fatty Acid-Derived Valuable Chemicals in Synthetic Microbes

    PubMed Central

    Yu, Ai-Qun; Pratomo Juwono, Nina Kurniasih; Leong, Susanna Su Jan; Chang, Matthew Wook

    2014-01-01

    Fatty acid derivatives, such as hydroxy fatty acids, fatty alcohols, fatty acid methyl/ethyl esters, and fatty alka(e)nes, have a wide range of industrial applications including plastics, lubricants, and fuels. Currently, these chemicals are obtained mainly through chemical synthesis, which is complex and costly, and their availability from natural biological sources is extremely limited. Metabolic engineering of microorganisms has provided a platform for effective production of these valuable biochemicals. Notably, synthetic biology-based metabolic engineering strategies have been extensively applied to refactor microorganisms for improved biochemical production. Here, we reviewed: (i) the current status of metabolic engineering of microbes that produce fatty acid-derived valuable chemicals, and (ii) the recent progress of synthetic biology approaches that assist metabolic engineering, such as mRNA secondary structure engineering, sensor-regulator system, regulatable expression system, ultrasensitive input/output control system, and computer science-based design of complex gene circuits. Furthermore, key challenges and strategies were discussed. Finally, we concluded that synthetic biology provides useful metabolic engineering strategies for economically viable production of fatty acid-derived valuable chemicals in engineered microbes. PMID:25566540

  15. Chemical Aspects of Astrophysically Observed Extraterrestrial Methanol, Hydrocarbon Derivatives, and Ions.

    PubMed

    Olah, George A; Mathew, Thomas; Prakash, G K Surya; Rasul, Golam

    2016-02-10

    Astrophysically observed extraterrestrial molecular matter contains, besides hydrogen and water, methane and methanol as the most abundant species. Feasible pathways and chemical aspects of their formation as well as of derived hydrocarbon homologues and their ions (carbocations and carbanions) are discussed on the basis of observed similarities with our studied terrestrial chemistry. The preferred pathway for converting extraterrestrial methane according to Ali et al. is based on CH5(+) and Olah's related nonclassical carbonium ion chemistry. On the basis of the observed higher reactivity of methanol compared with methane in various chemical reactions, a feasible new pathway is proposed for the conversion of extraterrestrial methanol to hydrocarbons, their derivatives, and carbocations together with a possible connection with methonium ion-based chemistry. PMID:26760052

  16. Special aspects of the temperature dependence of EPR absorption of chemically carbonized polyvinylidene fluoride derivatives

    NASA Astrophysics Data System (ADS)

    Zhivulin, V. E.; Pesin, L. A.; Ivanov, D. V.

    2016-01-01

    The temperature dependences of electron paramagnetic resonance (EPR) absorption of two samples of chemically carbonized derivatives of polyvinylidene fluoride (PVDF) synthesized under different conditions have been measured in the range of 100-300 K. It has been found that the temperature dependence of the integrated intensity of the EPR signal of both samples is nonmonotonic and does not obey the classical Curie dependence characteristic of free radicals. An analytical expression that is consistent with experimental data and suggests the presence of an activation component of paramagnetism in the test samples has been obtained. The presence of a term independent of temperature in this equation also indicates the paramagnetic contribution of free electrons. The magnitude of the activation energy of the singlet-triplet transitions has been evaluated: δ = 0.067 eV. The HYSCORE spectra of chemically carbonized PVDF derivatives have been obtained for the first time.

  17. Liquid-phase catalytic processing of biomass-derived oxygenated hydrocarbons to fuels and chemicals.

    PubMed

    Chheda, Juben N; Huber, George W; Dumesic, James A

    2007-01-01

    Biomass has the potential to serve as a sustainable source of energy and organic carbon for our industrialized society. The focus of this Review is to present an overview of chemical catalytic transformations of biomass-derived oxygenated feedstocks (primarily sugars and sugar-alcohols) in the liquid phase to value-added chemicals and fuels, with specific examples emphasizing the development of catalytic processes based on an understanding of the fundamental reaction chemistry. The key reactions involved in the processing of biomass are hydrolysis, dehydration, isomerization, aldol condensation, reforming, hydrogenation, and oxidation. Further, it is discussed how ideas based on fundamental chemical and catalytic concepts lead to strategies for the control of reaction pathways and process conditions to produce H(2)/CO(2) or H(2)/CO gas mixtures by aqueous-phase reforming, to produce furan compounds by selective dehydration of carbohydrates, and to produce liquid alkanes by the combination of aldol condensation and dehydration/hydrogenation processes. PMID:17659519

  18. An overview on chemical derivatization and stability aspects of selected avermectin derivatives.

    PubMed

    Awasthi, Atul; Razzak, Majid; Al-Kassas, Raida; Harvey, Joanne; Garg, Sanjay

    2012-01-01

    Naturally occurring avermectins (AVMs) and its derivatives are potent endectocide compounds, well-known for their novel mode of action against a broad range of nematode and anthropod animal parasites. In this review, chemical and pharmaceutical aspects of AVM derivatives are described including stability, synthetic and purification processes, impurities and degradation pathways, and subsequent suggestions are made to improve the chemical stability. It has been found out that unique structure of AVM molecules and presence of labile groups facilitated the derivatization of AVM into various compounds showing strong anthelmintic activity. However, the same unique structure is also responsible for labile nature related to sensitive stability profile of molecules. AVMs are found to be unstable in acidic and alkaline conditions. In addition, these compounds are sensitive to strong light, and subsequently presence of photo-isomer in animals treated topically with AVM product is well known. The pharmacoepial recommendations for addition of antioxidant into drug substance, as well as its products, arises from the fact that AVM are very sensitive to oxidation. Formations of solvates, salts, epoxides, reduction of double bonds and developing liquid formulation around pH 6.2, were some chemical approaches used to retard the degradation in AVM. This coherent review will contribute towards the better understanding of the correlation of chemical processes, stability profile and biological activity; therefore, it will help to design the shelf-life stable formulations containing AVMs. PMID:22863694

  19. Cardiac chemical constant. Part I: Derivation of the characteristic phenomenological equation.

    PubMed

    Phillips, C A

    1990-01-01

    A physiochemical parameter is derived and defined as the cardiac chemical equilibrium dissociation constant (KD). KD is based upon a phenomenological model in which the cardiac muscle chemical reaction kinetics describe the interconversion between long and short units (i.e. the individual sarcomere is fully extended or fully contracted). KD is defined as the ratio of the number of units in the long state to the number of units in the short state. The mathematical development proceeds through four stages: derivation of the governing differential equation during cardiac systole; simplification of the differential equation to describe the cardiac model; determination of the upper and lower limits and average value of Nt (the total number of units in a hypothetical mid-wall circumferential fibre): definition and calculation of the cardiac chemical constant (KD). KD is shown to describe a series of equilibrium points throughout cardiac systole. This requires that each mechanical equilibrium state (a series of static, steady-state intervals over time) is also associated with its own specific chemical equilibrium state. PMID:2296165

  20. Enantioseparation on Riboflavin Derivatives Chemically Bonded to Silica Gel as Chiral Stationary Phases for HPLC.

    PubMed

    Kumano, Daisuke; Iwahana, Soichiro; Iida, Hiroki; Shen, Chengshuo; Crassous, Jeanne; Yashima, Eiji

    2015-08-01

    Acetylated and/or 3,5-dimethylphenylcarbamated riboflavins were prepared and the resulting riboflavin derivatives as well as natural riboflavin were regioselectively immobilized on silica gel through chemical bonding at the 5'-O- or 3-N-position of the riboflavin to develop novel chiral stationary phases (CSPs) for enantioseparation by high-performance liquid chromatography (HPLC). The chiral recognition abilities of the obtained CSPs were significantly dependent on the structures of the riboflavin derivatives, the position of the chemical bonding on the silica gel, and the structures of the racemic compounds. The CSPs bonded at the 5'-O-position on the silica gel tended to well separate helicene derivatives, while the CSPs bonded at the 3-N-position composed of acetylated and 3,5-dimethylphenylcarbamated riboflavins showed a better resolving ability toward helicene derivatives and bulky aromatic racemic alcohols, respectively, and some of them were completely separated into the enantiomers. The observed difference in the chiral recognition abilities of these riboflavin-based CSPs is discussed based on the difference in their structures, including the substituents of riboflavin and the positions immobilized on the silica gel. PMID:25919938

  1. Inhibition of anthrax lethal factor by curcumin and chemically modified curcumin derivatives

    PubMed Central

    Zhang, Yu; Golub, Lorne M.; Johnson, Francis; Simon, Sanford R.

    2014-01-01

    Curcuma longa Curcumin (diferuloylmethane), the active ingredient in the eastern spice turmeric (Curcuma longa), has been shown to inhibit the activities of numerous enzymes and signaling molecules involved in cancer, bacterial and viral infections and inflammatory diseases. We have investigated the inhibitory activities of curcumin and chemically modified curcumin (CMC) derivatives toward lethal factor (LF), the proteolytic component of anthrax toxin produced by the bacterium Bacillus anthracis. Curcumin (Compound 1) appears to inhibit the catalytic activity of LF through a mixture of inhibitory mechanisms, without significant compromise to the binding of oligopeptide substrates, and one CMC derivative in particular, Compound 3 (4-phenylaminocarbonylbis-demethoxycurcumin), is capable of inhibiting LF with potency comparable with the parent compound, while also showing improved solubility and stability. The quantitative reduction in catalytic activity achieved by the different CMC derivatives appears to be a function of the proportion of the multiple mechanisms through which they inhibit the enzyme. PMID:24102525

  2. Use of chemical genomics in assessment of the UPR.

    PubMed

    Saito, Sakae; Tomida, Akihiro

    2011-01-01

    Glucose deprivation, one of the major physiological conditions in solid tumor, leads to activation of the unfolded protein response (UPR) in cancer cells. The UPR occurs through the transcriptional and translational regulatory mechanisms that improve the capacity of the endoplasmic reticulum (ER) to fold and traffic proteins and allows the cell to survive under stress conditions. We previously reported that the macrocyclic compound versipelostatin and the antidiabetic biguanides metformin, buformin, and phenformin could inhibit the UPR during glucose deprivation as well as induce the UPR by treatment of cells with 2-deoxy-d-glucose (2DG), a glycolysis inhibitor. Versipelostatin and biguanides show highly selective cytotoxicity to glucose-deprived tumor cells and exert in vivo antitumor activity; thus, these compounds would be interesting anticancer agent candidates. By microarray analysis, we demonstrated that cancer cells under glucose deprivation conditions caused activation of the UPR transcription program, which was suppressed broadly by versipelostatin and biguanides. We also identified the drug-driven gene signatures that can be used to discover pharmacologic UPR modulators. Indeed, we found several bioactive drugs, such as pyrvinium pamoate, valinomycin, and rottlerin, that selectively suppressed 2DG-induced GRP78 promoter activity as versipelostatin and biguanide did. Together with growing bioinformatics databases and analytical tools, our approach could provide a chemical genomic basis for developing UPR-targeting drugs against solid tumors. PMID:21329808

  3. Evaluation of Chemical Warfare Agent Percutaneous Vapor Toxicity: Derivation of Toxicity Guidelines for Assessing Chemical Protective Ensembles.

    SciTech Connect

    Watson, A.P.

    2003-07-24

    Percutaneous vapor toxicity guidelines are provided for assessment and selection of chemical protective ensembles (CPEs) to be used by civilian and military first responders operating in a chemical warfare agent vapor environment. The agents evaluated include the G-series and VX nerve agents, the vesicant sulfur mustard (agent HD) and, to a lesser extent, the vesicant Lewisite (agent L). The focus of this evaluation is percutaneous vapor permeation of CPEs and the resulting skin absorption, as inhalation and ocular exposures are assumed to be largely eliminated through use of SCBA and full-face protective masks. Selection of appropriately protective CPE designs and materials incorporates a variety of test parameters to ensure operability, practicality, and adequacy. One aspect of adequacy assessment should be based on systems tests, which focus on effective protection of the most vulnerable body regions (e.g., the groin area), as identified in this analysis. The toxicity range of agent-specific cumulative exposures (Cts) derived in this analysis can be used as decision guidelines for CPE acceptance, in conjunction with weighting consideration towards more susceptible body regions. This toxicity range is bounded by the percutaneous vapor estimated minimal effect (EME{sub pv}) Ct (as the lower end) and the 1% population threshold effect (ECt{sub 01}) estimate. Assumptions of exposure duration used in CPE certification should consider that each agent-specific percutaneous vapor cumulative exposure Ct for a given endpoint is a constant for exposure durations between 30 min and 2 hours.

  4. Surface chemical functionalities affect the behavior of human adipose-derived stem cells in vitro

    NASA Astrophysics Data System (ADS)

    Liu, Xujie; Feng, Qingling; Bachhuka, Akash; Vasilev, Krasimir

    2013-04-01

    This study examines the effect of surface chemical functionalities on the behavior of human adipose-derived stem cells (hASCs) in vitro. Plasma polymerized films rich in amine (sbnd NH2), carboxyl (sbnd COOH) and methyl (sbnd CH3), were generated on hydroxyapatite (HAp) substrates. The surface chemical functionalities were characterized by X-ray photoelectron spectroscopy (XPS). The ability of different substrates to absorb proteins was evaluated. The results showed that substrates modified with hydrophilic functional group (sbnd COOH and sbnd NH2) can absorb more proteins than these modified with more hydrophobic functional group (sbnd CH3). The behavior of human adipose-derived stem cells (hASCs) cultured on different substrates was investigated in vitro: cell counting kit-8 (CCK-8) analysis was used to characterize cell proliferation, scanning electronic microscopy (SEM) analysis was used to characterize cell morphology and alkaline phosphatase (ALP) activity analysis was used to account for differentiation. The results of this study demonstrated that the sbnd NH2 modified surfaces encourage osteogenic differentiation; the sbnd COOH modified surfaces promote cell adhesion and spreading and the sbnd CH3 modified surfaces have the lowest ability to induce osteogenic differentiation. These findings confirmed that the surface chemical states of biomaterials can affect the behavior of hASCs in vitro.

  5. Tyrosine-Specific Chemical Modification with in Situ Hemin-Activated Luminol Derivatives.

    PubMed

    Sato, Shinichi; Nakamura, Kosuke; Nakamura, Hiroyuki

    2015-11-20

    Tyrosine-specific chemical modification was achieved using in situ hemin-activated luminol derivatives. Tyrosine residues in peptide and protein were modified effectively with N-methylated luminol derivatives under oxidative conditions in the presence of hemin and H2O2. Both single and double modifications of the tyrosine residue occurred in the reaction of angiotensin II with N-methylated luminol derivative 9. Tyrosine-specific chemical modification of the model protein bovine serum albumin (BSA) revealed that the surface-exposed tyrosine residues were selectively modified with 9. We succeeded in the functionalization of several proteins using azide-conjugated compound 18 using alkyne-conjugated probes by copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC) or dibenzocyclooctyne (DBCO)-mediated copper-free click chemistry. This tyrosine-specific modification was orthogonal to conventional lysine modification by N-hydroxysuccinimide (NHS) ester, and dual functionalization by fluorescence modification of tyrosine residues and PEG modification of lysine residues was achieved without affecting the modification efficiency. PMID:26356088

  6. Biguanide-induced mitochondrial dysfunction yields increased lactate production and cytotoxicity of aerobically-poised HepG2 cells and human hepatocytes in vitro

    SciTech Connect

    Dykens, James A. Jamieson, Joseph; Marroquin, Lisa; Nadanaciva, Sashi; Billis, Puja A.; Will, Yvonne

    2008-12-01

    As a class, the biguanides induce lactic acidosis, a hallmark of mitochondrial impairment. To assess potential mitochondrial impairment, we evaluated the effects of metformin, buformin and phenformin on: 1) viability of HepG2 cells grown in galactose, 2) respiration by isolated mitochondria, 3) metabolic poise of HepG2 and primary human hepatocytes, 4) activities of immunocaptured respiratory complexes, and 5) mitochondrial membrane potential and redox status in primary human hepatocytes. Phenformin was the most cytotoxic of the three with buformin showing moderate toxicity, and metformin toxicity only at mM concentrations. Importantly, HepG2 cells grown in galactose are markedly more susceptible to biguanide toxicity compared to cells grown in glucose, indicating mitochondrial toxicity as a primary mode of action. The same rank order of potency was observed for isolated mitochondrial respiration where preincubation (40 min) exacerbated respiratory impairment, and was required to reveal inhibition by metformin, suggesting intramitochondrial bio-accumulation. Metabolic profiling of intact cells corroborated respiratory inhibition, but also revealed compensatory increases in lactate production from accelerated glycolysis. High (mM) concentrations of the drugs were needed to inhibit immunocaptured respiratory complexes, supporting the contention that bioaccumulation is involved. The same rank order was found when monitoring mitochondrial membrane potential, ROS production, and glutathione levels in primary human hepatocytes. In toto, these data indicate that biguanide-induced lactic acidosis can be attributed to acceleration of glycolysis in response to mitochondrial impairment. Indeed, the desired clinical outcome, viz., decreased blood glucose, could be due to increased glucose uptake and glycolytic flux in response to drug-induced mitochondrial dysfunction.

  7. Ag electrode modified with polyhexamethylene biguanide stabilized silver nanoparticles: a new type of SERS substrates for detection of enzymatically generated thiocholine

    NASA Astrophysics Data System (ADS)

    Tepanov, A. A.; Nechaeva, N. L.; Prokopkina, T. A.; Kudrinskiy, A. A.; Kurochkin, I. N.; Lisichkin, G. V.

    2015-11-01

    The detection of thiocholine is one of the most widespread techniques for estimation of the cholinesterase activity – acetylcholinesterase and butyrylcholinesterase. Both cholinesterases can be inhibited by organophosphates and carbamates and accordingly can be considered for estimation of these pollutants in the environment. In the current work, SERS spectroscopy was applied for the thiocholine detection. The Ag electrodes modified with silver nanoparticles stabilized by polyhexamethylene biguanide were for the first time suggested as SERS-substrates for that purpose. Such electrodes can be applicable for SERS detection of submicromolar concentrations of thiocholine.

  8. Feasibility study of the natural derived chitosan dialdehyde for chemical modification of collagen.

    PubMed

    Liu, Xinhua; Dan, Nianhua; Dan, Weihua; Gong, Juxia

    2016-01-01

    The aim of this study is to evaluate the chemical crosslinking effects of the natural derived chitosan dialdehyde (OCS) on collagen. Fourier transform infrared (FTIR) spectroscopy, differential scanning calorimetry (DSC) and circular dichroism (CD) measurements suggest that introducing OCS might not destroy the natural triple helix conformation of collagen but enhance the thermal-stability of collagen. Meanwhile, a denser fibrous network of cross-linked collagen is observed by atomic force microscopy. Further, scanning electron microscopy (SEM) and aggregation kinetics analysis confirm that the fibrillation process of collagen advances successfully and OCS could lengthen the completion time of collagen fibrillogenesis but raise the reconstitution rate of collagen fibrils or microfibrils. Besides, the cytocompatibility analysis implies that when the dosage of OCS is less than 15%, introducing OCS into collagen might be favorable for the cell's adhesion, growth and proliferation. Taken as a whole, the present study demonstrates that OCS might be an ideal crosslinker for the chemical fixation of collagen. PMID:26562557

  9. Literature-derived absorption coefficients for 39 chemicals via oral and inhalation routes of exposure.

    PubMed

    Owen, B A

    1990-06-01

    Absorption refers to the amount of a chemical or substance that is able to cross biological membranes and be taken up by the blood for subsequent distribution to target tissues. The term absorption coefficient, as used here, is a numerical descriptor characterizing that fractional uptake by the blood and represents an approximation of the biological "dose" ultimately responsible for toxicity or other effects following exposure or chemical administration. Regulatory agencies utilize absorption coefficients in deriving acceptable daily intake values and health advisory indices, as well as in quantifying radiological risk. However, absorption coefficients do not exist for many chemicals due to a paucity of appropriate toxicological data. As a result, regulatory policy must often provide default options that assume, for example, 100% absorption by all routes to permit evaluation of "data-gap" chemicals. This paper attempts to improve the situation by providing a discrete source of route-specific absorption coefficients that are based on experimental data reported in the open literature. The estimates presented here are the result of an extensive investigation of three data bases (TOXLINE, HSDB, and CIS), many agency documents, and nearly 200 articles from 30 scientific journals. Acknowledging that absorption efficiency varies with dietary status, age, and several other situation-specific factors, the estimates presented here are intended to reflect absorption by the average adult human. PMID:2196635

  10. Chemically defined conditions for human iPS cell derivation and culture

    PubMed Central

    Chen, Guokai; Gulbranson, Daniel R.; Hou, Zhonggang; Bolin, Jennifer M.; Ruotti, Victor; Probasco, Mitchell D.; Smuga-Otto, Kimberly; Howden, Sara E.; Diol, Nicole R.; Propson, Nicholas E.; Wagner, Ryan; Lee, Garrett O.; Antosiewicz-Bourget, Jessica; Teng, Joyce M. C.; Thomson, James A.

    2011-01-01

    We reexamine the individual components for human ES and iPS cell culture, and formulate a cell culture system in which all protein reagents for liquid media, attachment surfaces, and splitting are chemically defined. A major improvement is the lack of a serum albumin component, as variations in either animal or human sourced albumin batches have previously plagued human ES and iPS cell culture with inconsistencies. Using this new medium (E8) and vitronectin-coated surfaces, we demonstrate improved derivation efficiencies of vector-free human iPS cells with an episomal approach. This simplified E8 medium should facilitate both the research use and clinical applications of human ES and iPS cells and their derivatives, and should be applicable to other reprogramming methods. PMID:21478862

  11. Hydrodeoxygenation processes: advances on catalytic transformations of biomass-derived platform chemicals into hydrocarbon fuels.

    PubMed

    De, Sudipta; Saha, Basudeb; Luque, Rafael

    2015-02-01

    Lignocellulosic biomass provides an attractive source of renewable carbon that can be sustainably converted into chemicals and fuels. Hydrodeoxygenation (HDO) processes have recently received considerable attention to upgrade biomass-derived feedstocks into liquid transportation fuels. The selection and design of HDO catalysts plays an important role to determine the success of the process. This review has been aimed to emphasize recent developments on HDO catalysts in effective transformations of biomass-derived platform molecules into hydrocarbon fuels with reduced oxygen content and improved H/C ratios. Liquid hydrocarbon fuels can be obtained by combining oxygen removal processes (e.g. dehydration, hydrogenation, hydrogenolysis, decarbonylation etc.) as well as by increasing the molecular weight via C-C coupling reactions (e.g. aldol condensation, ketonization, oligomerization, hydroxyalkylation etc.). Fundamentals and mechanistic aspects of the use of HDO catalysts in deoxygenation reactions will also be discussed. PMID:25443804

  12. Expedited access to vinaxanthone and chemically edited derivatives possessing neuronal regenerative effects through ynone coupling reactions.

    PubMed

    Chin, Matthew R; Zlotkowski, Katherine; Han, Michelle; Patel, Saagar; Eliasen, Anders M; Axelrod, Abram; Siegel, Dionicio

    2015-04-15

    The natural product vinaxanthone has demonstrated a remarkable capability to promote nerve growth following injury or transplantation. In rats following total transection of the spinal cord delivery of vinaxanthone enhanced axonal regeneration, remyelination and angiogenesis at the site of injury all leading to an improved reinstatement of motor function. Through the development of a new ynone coupling reaction, chemically edited derivatives of vinaxanthone have been prepared and studied for improved activity. The coupling reaction allows rapid access to new derivatives, wherein n ynone precursors provide n(2) vinaxanthone analogues. These compounds have been tested for their ability to promote neuronal regrowth using laser axotomy, severing axonal connections in Caenorhabditis elegans. This precise microsurgery using C. elegans allows a new in vivo approach for medicinal chemistry based optimization of neuronal growth promoting compounds. PMID:25615693

  13. Derivation of the chemical-equilibrium rate coefficient using scattering theory

    NASA Technical Reports Server (NTRS)

    Mickens, R. E.

    1977-01-01

    Scattering theory is applied to derive the equilibrium rate coefficient for a general homogeneous chemical reaction involving ideal gases. The reaction rate is expressed in terms of the product of a number of normalized momentum distribution functions, the product of the number of molecules with a given internal energy state, and the spin-averaged T-matrix elements. An expression for momentum distribution at equilibrium for an arbitrary molecule is presented, and the number of molecules with a given internal-energy state is represented by an expression which includes the partition function.

  14. Hierarchy of Electronic Properties of Chemically Derived and Pristine Graphene Probed by Microwave Imaging

    SciTech Connect

    Kundhikanjana, W.

    2010-06-02

    Local electrical imaging using microwave impedance microscope is performed on graphene in different modalities, yielding a rich hierarchy of the local conductivity. The low-conductivity graphite oxide and its derivatives show significant electronic inhomogeneity. For the conductive chemical graphene, the residual defects lead to a systematic reduction of the microwave signals. In contrast, the signals on pristine graphene agree well with a lumped-element circuit model. The local impedance information can also be used to verify the electrical contact between overlapped graphene pieces.

  15. Chemical constituents of marine mangrove-derived endophytic fungus Alternaria tenuissima EN-192

    NASA Astrophysics Data System (ADS)

    Sun, Hong; Gao, Shushan; Li, Xiaoming; Li, Chunshun; Wang, Bingui

    2013-03-01

    A chemical investigation of the ethyl acetate extract of the fermentation broth of Alternaria tenuissima EN-192, an endophytic fungus obtained from the stems of the marine mangrove plant Rhizophora stylosa, resulted in the isolation of nine known secondary metabolites, including four indole-diterpenoids: penijanthine A ( 1), paspaline ( 2), paspalinine ( 3), and penitrem A ( 4); three tricycloalternarene derivatives: tricycloalternarene 3a ( 5), tricycloalternarene 1b ( 6), and tricycloalternarene 2b ( 7); and two alternariol congeners: djalonensone ( 8) and alternariol ( 9). The chemical structures of these metabolites were characterized through a combination of detailed spectroscopic analyses and their comparison with reports from the literature. The inhibitory activities of each isolated compound against four bacteria were evaluated and compounds 5 and 8 displayed moderate activity against the aquaculture pathogenic bacterium Vibrio anguillarum, with inhibition zone diameters of 8 and 9 mm, respectively, at 100 μg/disk. To the best of our knowledge, this is the first report on the secondary metabolites of mangrove-derived A lternaria tenuissima and also the first report of the isolation of indole-diterpenoids from fungal genus A lternaria.

  16. Combined physical-chemical and aerobic biological treatments of wastewater derived from sauce manufacturing.

    PubMed

    Martn, M A; Gonzlez, I; Siles, J A; Berrios, M; Martn, A

    2013-04-01

    The viability of an integrated coagulation-flocculation and aerobic treatment for purifying wastewater derived from a sauce manufacturing industry was evaluated. The best coagulation-flocculation results were obtained at alkaline pH, showing the greatest turbidity removal efficiency (greater than 90%) and a total chemical oxygen demand (COD) removal of approximately 80%, Additionally, experiments at alkaline pH reduce the reagent requirements (coagulant concentration of 0.4 mL/L and flocculant concentration of 4.0 mL/L) providing a consequent economic benefit as compared to experiments at neutral and acidic pH. Another set of experiments was conducted in a sequencing batch reactor to evaluate the aerobic biodegradability of the remnant dissolved organic matter. The effluent from the physical-chemical pre-treatment at alkaline pH again showed the highest biodegradability (76%), with a global COD total removal of 98%. The results showed that the combination of both techniques could be a viable alternative to efficiently treat wastewater derived from sauce manufacturing. PMID:23697239

  17. Determination of the Chemical Structures of Tandyukisins B–D, Isolated from a Marine Sponge-Derived Fungus

    PubMed Central

    Yamada, Takeshi; Umebayashi, Yoshihide; Kawashima, Maiko; Sugiura, Yuma; Kikuchi, Takashi; Tanaka, Reiko

    2015-01-01

    Tandyukisins B–D (1–3), novel decalin derivatives, have been isolated from a strain of Trichoderma harzianum OUPS-111D-4 originally derived from the marine sponge Halichondria okadai, and their structures have been elucidated on the basis of spectroscopic analyses using 1D and 2D NMR techniques. In addition, their chemical structures were established by chemical transformation. They exhibited weak cytotoxicity, but selective growth inhibition on panel screening using 39 human cancer cell lines. PMID:26006715

  18. Determination of the chemical structures of tandyukisins B-D, isolated from a marine sponge-derived fungus.

    PubMed

    Yamada, Takeshi; Umebayashi, Yoshihide; Kawashima, Maiko; Sugiura, Yuma; Kikuchi, Takashi; Tanaka, Reiko

    2015-05-01

    Tandyukisins B-D (1-3), novel decalin derivatives, have been isolated from a strain of Trichoderma harzianum OUPS-111D-4 originally derived from the marine sponge Halichondria okadai, and their structures have been elucidated on the basis of spectroscopic analyses using 1D and 2D NMR techniques. In addition, their chemical structures were established by chemical transformation. They exhibited weak cytotoxicity, but selective growth inhibition on panel screening using 39 human cancer cell lines. PMID:26006715

  19. Targeted delivery and improved therapeutic potential of catalase by chemical modification: combination with superoxide dismutase derivatives.

    PubMed

    Yabe, Y; Nishikawa, M; Tamada, A; Takakura, Y; Hashida, M

    1999-05-01

    Four types of bovine liver catalase (CAT) derivatives, succinylated (Suc-CAT), galactosylated (Gal-CAT), mannosylated (Man-CAT), and polyethylene glycol conjugate (PEG-CAT), were synthesized and their pharmacokinetics and therapeutic potential in a hepatic ischemia/reperfusion injury model were studied in mice. About 90% of the CAT enzymatic activity was retained after chemical modification. Biodistribution studies showed that 111indium (111In)-Gal-CAT accumulated selectively in the liver parenchymal cells as 111In-CAT, whereas an increased amount of 111In-Suc-CAT and 111In-Man-CAT was delivered to liver nonparenchymal cells. 111In-PEG-CAT exhibited prolonged retention in plasma. Pharmacokinetic analysis revealed that the hepatic uptake clearances of 111In-Suc-CAT, 111In-Gal-CAT, and 111In-Man-CAT were much greater than that of 111In-CAT, whereas that of 111In-PEG-CAT was very small. In the ischemia/reperfusion injury model, in which hepatic injury was induced by occlusion of the portal vein for 30 min followed by 1 h reperfusion, the elevation of plasma glutamic pyruvic transaminase and glutamic oxaloacetic transaminase levels was slightly inhibited by treatment with native CAT or Gal-CAT. PEG-CAT was less potent. In contrast, Suc-CAT and Man-CAT effectively suppressed the increase in plasma glutamic pyruvic transaminase and glutamic oxaloacetic transaminase. Coinjection of mannosylated superoxide dismutase marginally improved the inhibitory effects of CAT derivatives. These results demonstrate that targeted CAT delivery to liver nonparenchymal cells via chemical modification is a promising approach to prevent hepatic injuries caused by reactive oxygen species. The potential usefulness of combining of CAT and superoxide dismutase derivatives is also demonstrated. PMID:10215702

  20. Chemical transformation of CO2 during its capture by waste biomass derived biochars.

    PubMed

    Xu, Xiaoyun; Kan, Yue; Zhao, Ling; Cao, Xinde

    2016-06-01

    Biochar is a porous carbonaceous material with high alkalinity and rich minerals, making it possible for CO2 capture. In this study, biochars derived from pig manure, sewage sludge, and wheat straw were evaluated for their CO2 sorption behavior. All three biochars showed high sorption abilities for CO2, with the maximum capacities reaching 18.2-34.4 mg g(-1) at 25 °C. Elevating sorption temperature and moisture content promoted the transition of CO2 uptake from physical to chemical process. Mineral components such as Mg, Ca, Fe, K, etc. in biochar induced the chemical sorption of CO2 via the mineralogical reactions which occupied 17.7%-50.9% of the total sorption. FeOOH in sewage sludge biochar was transformed by sorbed CO2 into Fe(OH)2CO3, while the sorbed CO2 in pig manure biochar was precipitated as K2Ca(CO3)2 and CaMg(CO3)2, which resulted in a dominant increase of insoluble inorganic carbon in both biochars. For wheat straw biochar, sorbed CO2 induced CaCO3 transformed into soluble Ca(HCO3)2, which led to a dominant increase of soluble inorganic carbons. The results obtained from this study demonstrated that biochar as a unique carbonaceous material could distinctly be a promising sorbent for CO2 capture in which chemical sorption induced by mineralogical reactions played an important role. PMID:26995449

  1. Metabolic engineering of Saccharomyces cerevisiae for production of fatty acid-derived biofuels and chemicals.

    PubMed

    Runguphan, Weerawat; Keasling, Jay D

    2014-01-01

    As the serious effects of global climate change become apparent and access to fossil fuels becomes more limited, metabolic engineers and synthetic biologists are looking towards greener sources for transportation fuels. In recent years, microbial production of high-energy fuels by economically efficient bioprocesses has emerged as an attractive alternative to the traditional production of transportation fuels. Here, we engineered the budding yeast Saccharomyces cerevisiae to produce fatty acid-derived biofuels and chemicals from simple sugars. Specifically, we overexpressed all three fatty acid biosynthesis genes, namely acetyl-CoA carboxylase (ACC1), fatty acid synthase 1 (FAS1) and fatty acid synthase 2 (FAS2), in S. cerevisiae. When coupled to triacylglycerol (TAG) production, the engineered strain accumulated lipid to more than 17% of its dry cell weight, a four-fold improvement over the control strain. Understanding that TAG cannot be used directly as fuels, we also engineered S. cerevisiae to produce drop-in fuels and chemicals. Altering the terminal "converting enzyme" in the engineered strain led to the production of free fatty acids at a titer of approximately 400 mg/L, fatty alcohols at approximately 100mg/L and fatty acid ethyl esters (biodiesel) at approximately 5 mg/L directly from simple sugars. We envision that our approach will provide a scalable, controllable and economic route to this important class of chemicals. PMID:23899824

  2. Chemical and molecular aspects on interactions of galanthamine and its derivatives with cholinesterases.

    PubMed

    Gulcan, Hayrettin O; Orhan, Ilkay E; Sener, Bilge

    2015-01-01

    Dual action of galanthamine as potent cholinesterase inhibitor and nicotinic modulator has attracted a great attention to be used in the treatment of AD. Consequently, galanthamine, a natural alkaloid isolated from a Galanthus species (snowdrop, Amaryllidaceae), has become an attractive model compound for synthesis of its novel derivatives to discover new drug candidates. Numerous studies have been done to elucidate interactions between galanthamine and its different derivatives and the enzymes; acetylcholinesterase (AChE) and butyrylcholinesterase (BChE) using in vitro and in silico experimental models. The in vitro studies revealed that galanthamine inhibits AChE in strong, competitive, long-acting, and reversible manner as well as BChE, although its selectivity towards AChE is much higher than BChE. The in silico studies carried out by employing molecular docking experiments as well as molecular dynamics simulations pointed out to existence of strong interactions of galanthamine with the active gorge of AChE, mostly of Torpedo californica (the Pasific electric ray) origin. In this review, we evaluate the mainstays of cholinesterase inhibitory action of galanthamine and its various derivatives from the point of view of chemical and molecular aspects. PMID:25483718

  3. Biomass-derived Syngas Utilization for Fuels and Chemicals - Final Report

    SciTech Connect

    David C. Dayton

    2010-03-24

    Executive Summary The growing gap between petroleum production and demand, mounting environmental concerns, and increasing fuel prices have stimulated intense interest in research and development (R&D) of alternative fuels, both synthetic and bio-derived. Currently, the most technically defined thermochemical route for producing alternative fuels from lignocellulosic biomass involves gasification/reforming of biomass to produce syngas (carbon monoxide [CO] + hydrogen [H2]), followed by syngas cleaning, Fischer-Tropsch synthesis (FTS) or mixed alcohol synthesis, and some product upgrading via hydroprocessing or separation. A detailed techno-economic analysis of this type of process has recently been published [1] and it highlights the need for technical breakthroughs and technology demonstration for gas cleanup and fuel synthesis. The latter two technical barrier areas contribute 40% of the total thermochemical ethanol cost and 70% of the production cost, if feedstock costs are factored out. Developing and validating technologies that reduce the capital and operating costs of these unit operations will greatly reduce the risk for commercializing integrated biomass gasification/fuel synthesis processes for biofuel production. The objective of this project is to develop and demonstrate new catalysts and catalytic processes that can efficiently convert biomass-derived syngas into diesel fuel and C2-C4 alcohols. The goal is to improve the economics of the processes by improving the catalytic activity and product selectivity, which could lead to commercialization. The project was divided into 4 tasks: Task 1: Reactor Systems: Construction of three reactor systems was a project milestone. Construction of a fixed-bed microreactor (FBR), a continuous stirred tank reactor (CSTR), and a slurry bubble column reactor (SBCR) were completed to meet this milestone. Task 2: Iron Fischer-Tropsch (FT) Catalyst: An attrition resistant iron FT catalyst will be developed and tested. Task 3: Chemical Synthesis: Promising process routes will be identified for synthesis of selected chemicals from biomass-derived syngas. A project milestone was to select promising mixed alcohol catalysts and screen productivity and performance in a fixed bed micro-reactor using bottled syngas. This milestone was successfully completed in collaboration withour catalyst development partner. Task 4: Modeling, Engineering Evaluation, and Commercial Assessment: Mass and energy balances of conceptual commercial embodiment for FT and chemical synthesis were completed.

  4. Quantum chemical investigations on the nonradiative deactivation pathways of cytosine derivatives.

    PubMed

    Nakayama, Akira; Yamazaki, Shohei; Taketsugu, Tetsuya

    2014-10-01

    The nonradiative deactivation pathways of cytosine derivatives (cytosine, 5-fluorocytosine, 5-methylcytosine, and 1-methycytosine) and their tautomers are investigated by quantum chemical calculations, and the substituent effects on the deactivation process are examined. The MS-CASPT2 method is employed in the excited-state geometry optimization and also in the search for conical intersection points, and the potential energy profiles connecting the Franck-Condon point, excited-state minimum energy structures, and the conical intersection points are investigated. Our calculated vertical and adiabatic excitation energies are in quite good agreement with the experimental results, and the relative barrier heights leading to the conical intersections are correlated with the experimentally observed excite-state lifetimes, where the calculated barrier heights are in the order of cytosine < 5-methylcytosine < 5-fluorocytosine. PMID:25178384

  5. Evaluation of alcoholic hydroxyl derivatives for chemically amplified extreme ultraviolet resist

    NASA Astrophysics Data System (ADS)

    Furukawa, Kikuo; Kozawa, Takahiro; Tagawa, Seiichi

    2009-03-01

    Extreme ultraviolet (EUV) lithography is the most favorable process as next-generation lithography. For the development of EUV resists, phenolic materials such as poly (4-hydroxystyrene) have been investigated. Phenolic hydroxyl groups of polymers play an important role in acid diffusion, dissolution kinetics, and adhesion to substrates. Besides these important roles, phenolic hydroxyl groups are also an effective proton source in acid generation in EUV resists. However, the roles of alcohol hydroxyl groups have not been well-studied. To clarify the difference between phenolic and alcoholic hydroxyl groups upon exposure to EUV radiation, we synthesized acrylic terpolymers containing alcoholic hydroxyl groups as model photopolymers and exposed the resist samples based on these polymers to EUV radiation. On the basis of the lithographic performances of these resist samples, we evaluated the characteristics of alcoholic hydroxyl groups upon exposure to EUV radiation. We discuss the relationship between the chemical structures of these derivatives and lithographic performance.

  6. An overview on chemical aspects and potential health benefits of limonoids and their derivatives.

    PubMed

    Tundis, Rosa; Loizzo, Monica Rosa; Menichini, Francesco

    2014-01-01

    Limonoids are heavily oxygenated, modified triterpenes dominant in Meliaceae and Rutaceae plant families. The term 'limonoid' is derived from limonin, which was first identified as the bitter constituent of Citrus seeds in 1841. This group of secondary metabolites exhibits a wide range of biological properties, including anticancer, antibacterial, antifungal, antimalarial, and antiviral activities. Significant progress on the role of limonoids as promising candidates for cancer chemoprevention and/or therapy has been achieved in particular in recent years. The aim of this review article is to discuss the recent developments on limonoids chemical aspects and biological activities with the relationship between structure and activity, supporting the new possibilities for the medicinal and/or nutraceutical use of these compounds. PMID:24188270

  7. Fatty Acid-Derived Biofuels and Chemicals Production in Saccharomyces cerevisiae.

    PubMed

    Zhou, Yongjin J; Buijs, Nicolaas A; Siewers, Verena; Nielsen, Jens

    2014-01-01

    Volatile energy costs and environmental concerns have spurred interest in the development of alternative, renewable, sustainable, and cost-effective energy resources. Environment-friendly processes involving microbes can be used to synthesize advanced biofuels. These fuels have the potential to replace fossil fuels in supporting high-power demanding machinery such as aircrafts and trucks. From an engineering perspective, the pathway for fatty acid biosynthesis is an attractive route for the production of advanced fuels such as fatty acid ethyl esters, fatty alcohols, and alkanes. The robustness and excellent accessibility to molecular genetics make the yeast Saccharomyces cerevisiae a suitable host for the purpose of bio-manufacturing. Recent advances in metabolic engineering, as well as systems and synthetic biology, have now provided the opportunity to engineer yeast metabolism for the production of fatty acid-derived fuels and chemicals. PMID:25225637

  8. Fatty Acid-Derived Biofuels and Chemicals Production in Saccharomyces cerevisiae

    PubMed Central

    Zhou, Yongjin J.; Buijs, Nicolaas A.; Siewers, Verena; Nielsen, Jens

    2014-01-01

    Volatile energy costs and environmental concerns have spurred interest in the development of alternative, renewable, sustainable, and cost-effective energy resources. Environment-friendly processes involving microbes can be used to synthesize advanced biofuels. These fuels have the potential to replace fossil fuels in supporting high-power demanding machinery such as aircrafts and trucks. From an engineering perspective, the pathway for fatty acid biosynthesis is an attractive route for the production of advanced fuels such as fatty acid ethyl esters, fatty alcohols, and alkanes. The robustness and excellent accessibility to molecular genetics make the yeast Saccharomyces cerevisiae a suitable host for the purpose of bio-manufacturing. Recent advances in metabolic engineering, as well as systems and synthetic biology, have now provided the opportunity to engineer yeast metabolism for the production of fatty acid-derived fuels and chemicals. PMID:25225637

  9. Preparation of functional composite materials based on chemically derived graphene using solution process

    NASA Astrophysics Data System (ADS)

    Kim, M.; Hyun, W. J.; Mun, S. C.; Park, O. O.

    2015-04-01

    Chemically derived graphenes were assembled into functional composite materials using solution process from stable solvent dispersion. We have developed foldable electronic circuits on paper substrates using vacuum filtration of graphene nanoplates dispersion and a selective transfer process without need for special equipment. The electronic circuits on paper substrates revealed only a small change in conductance under various folding angles and maintained an electronic path after repetitive folding and unfolding. We also prepared flexible. binder-free graphene paper-like materials by addition of graphene oxide as a film stabilizer. This graphene papers showed outstanding electrical conductivity up to 26,000 S/m and high charge capacity as an anode in lithium-ion battery without any post-treatments. For last case, multi-functional thin film structures of graphene nanoplates were fabricated by using layer-by-layer assembly technique, showing optical transparency, electrical conductivity and enhanced gas barrier property.

  10. Chemical Signals of Synthetic Disaccharide Derivatives Dominate Rhamnolipids at Controlling Multiple Bacterial Activities.

    PubMed

    Singh, Nischal; Shetye, Gauri S; Zheng, Hewen; Sun, Jiayue; Luk, Yan-Yeung

    2016-01-01

    Microbes secrete molecules that modify their environment. Here, we demonstrate a class of synthetic disaccharide derivatives (DSDs) that mimics and dominates the activity of naturally secreted rhamnolipids by Pseudomonas aeruginosa. The DSDs exhibit the dual function of activating and inhibiting the swarming motility through a concentration-dependent activity reversal that is characteristic of signaling molecules. Whereas DSDs tethered with a saturated farnesyl group exhibit inhibition of both biofilm formation and swarming motility, with higher activities than rhamnolipids, a saturated farnesyl tethered with a sulfonate group only inhibits swarming motility but promote biofilm formation. These results identified important structural elements for controlling swarming motility, biofilm formation, and bacterial adhesion and suggest an effective chemical approach to control intertwined signaling processes that are important for biofilm formation and motilities. PMID:26511780

  11. Analytical characterization of plasma membrane-derived vesicles produced via osmotic and chemical vesiculation.

    PubMed

    Sarabipour, Sarvenaz; Chan, Robin B; Zhou, Bowen; Di Paolo, Gilbert; Hristova, Kalina

    2015-07-01

    Plasma membrane-derived vesicles are being used in biophysical and biochemical research as a simple, yet native-like model of the cellular membrane. Here we report on the characterization of vesicles produced via two different vesiculation methods from CHO and A431 cell lines. The first method is a recently developed method which utilizes chloride salts to induce osmotic vesiculation. The second is a well established chemical vesiculation method which uses DTT and formaldehyde. We show that both vesiculation methods produce vesicles which contain the lipid species previously reported in the plasma membrane of these cell lines. The two methods lead to small but statistically significant differences in two lipid species only; phosphatidylcholine (PC) and plasmalogen phosphatidylethanolamine (PEp). However, highly significant differences were observed in the degree of incorporation of a membrane receptor and in the degree of retention of soluble cytosolic proteins within the vesicles. PMID:25896659

  12. Total chemical synthesis of a ribozyme derived from a group I intron.

    PubMed Central

    Whoriskey, S K; Usman, N; Szostak, J W

    1995-01-01

    We describe the complete chemical synthesis of a ribozyme that catalyzes template-directed oligonucleotide ligation. The specific activity of the synthetic ribozyme is nearly identical to that of the same enzyme generated by in vitro transcription with T7 RNA polymerase. The ribozyme is derived from a group I intron and consists of three RNA fragments of 36, 43, and 59 nt that self-assemble to form a catalytically active complex. We have site-specifically substituted ribonucleotide analogs into this enzyme and have identified two 2'-hydroxyl groups that are required for full catalytic activity. In contrast, neither the 2'-hydroxyl nor the exocyclic amino group of the conserved guanosine in the guanosine binding site is necessary for catalysis. By allowing the ribozyme to be modified as easily as its substrates, this synthetic ribozyme system should be useful for testing specific hypotheses concerning ribozyme-substrate interactions and tertiary interactions within the ribozyme. Images Fig. 2 Fig. 3 PMID:7708666

  13. Biodistribution profiling of the chemical modified hyaluronic acid derivatives used for oral delivery system.

    PubMed

    Hsieh, Chien-Ming; Huang, Yu-Wen; Sheu, Ming-Thau; Ho, Hsiu-O

    2014-03-01

    A series of adipic acid dihydrazide (ADH)-modified hyaluronic acid (HA-ADH) compounds were synthesized and conjugated with QDots (QDots-HA conjugates) to assess the effects of the molecular weight (MW) and extent of chemical modification of HA on its biodistribution. Their physicochemical structures were confirmed by complementary application of GPC, (1)H NMR, FTIR, and UV-vis spectroscopic methods. In vivo imaging of QDots-HA conjugates after oral administration was analyzed to investigate their biodistribution in nude mice. Simultaneously, real-time bioimaging was confirmed by an anatomical analysis to investigate the organ-specific accumulation of conjugates. QDot-HA conjugates with a higher MW of HA or high modification presented relatively slow clearance leading to an extension of the retention time for up to 10 days, whereas those with lower MWs of HA or a low modification extent exhibited quick absorption and elimination after oral administration. Taken together, HA derivatives with suitable MWs and chemical modification extents can be used to design new, more-sophisticated, and intelligent HA-based vehicles for oral delivery with diverse characteristics. PMID:24315950

  14. Physical, morphological, and chemical studies of dusts derived from the machining of composite-epoxy materials.

    PubMed

    Boatman, E S; Covert, D; Kalman, D; Luchtel, D; Omenn, G S

    1988-04-01

    This work (in three parts) inquires into whether respirable dusts derived from the machining of six composite-epoxy materials (e.g., aircraft industry) may pose a health risk to the operators. Dust samples representative of a variety of composites and structural components were aerodynamically sized and fractionated. Bulk and fractionated samples were examined by light and electron microscopy and analyzed chemically by thermogravimetry (TGA), gas chromatography (GC) and mass spectrometry (MS). Relative fractions of respirable to total mass of bulk samples were less than 3%; aerodynamic diameters of fractionated particles ranged from 0.8 to 2.0 microns. By microscopy, bulk particles ranged from 7 to 11 microns in diameter, with mean aspect ratios from 4 to 8:1. Mean diameter of fractionated particles was 2.7 microns. By TGA, weight losses were negligible below 250 degrees C and variable but elevated at temperatures up to 860 degrees C. In assays of vapors released at 250 degrees C, GC/MS indicated a variety of compounds in different amounts for each sample. We conclude that under the present machining protocols, dusts at the tool face contained few particles of respirable size with no evidence of splitting of fibers longitudinally and were of a low volatilizable chemical content. Overall, composites were judged to be well cured and thermally stable. PMID:3349976

  15. Investigation of reports of sexual dysfunction among male chemical workers manufacturing stilbene derivatives

    SciTech Connect

    Quinn, M.M.; Wegman, D.H.; Greaves, I.A.; Hammond, S.K.; Ellenbecker, M.J.; Spark, R.F.; Smith, E.R. )

    1990-01-01

    A Health Hazard Evaluation was conducted by the National Institute for Occupational Safety and Health in an area of a large chemical plant that manufactured the stilbene derivative 4,4'-diaminostilbene-2,2'-disulfonic acid, an intermediate used for the production of optical brightening agents. Men employed in the area reported problems with impotence. The study population consisted of 44 men aged 20-57 years (mean age 37) employed in the area at the time of the evaluation. An industrial hygiene investigation, health and work history questionnaire survey, physical examinations, and blood chemistry and serum hormone evaluation were conducted. Fourteen percent of the men reported symptoms of impotence over the preceding 6 or more months, 7% had potency problems of shorter duration, and 7% were not currently impotent but had experienced impotence for 6 or more months in the past; 36% experienced decreased libido, all since beginning work in the production area. Low levels of serum testosterone (less than 350 ng/dl) were observed in 37% of the men. The low serum testosterone concentrations were not accounted for fully by diurnal variation or an effect of rotating shift work. It is suggested that exposures to chemicals possessing estrogenic activity may be related to the observed health effects in these workers.

  16. Degree of polymerization of 5,6-dihydroxyindole-derived eumelanin from chemical degradation study.

    PubMed

    Okuda, Hidekazu; Yoshino, Kyoji; Wakamatsu, Kazumasa; Ito, Shosuke; Sota, Takayuki

    2014-07-01

    Eumelanin is a brown-black pigment comprising 5,6-dihydroxyindole (DHI) and its 2-carboxy derivative (DHICA), but the detailed structure of eumelanin is unclear. Chemical degradation is a powerful tool for analyzing melanin. H2 O2 oxidation degradation of eumelanin affords pyrrole-2,3,5-tricarboxylic acid (PTCA) and pyrrole-2,3-dicarboxylic acid (PDCA). The ratio of PDCA to PTCA provides information about the eumelanin structure. In this article, we propose simple equations on the basis of previous experimental results on dimer yields for evaluating the yields of PTCA and PDCA from any DHI oligomers. Assuming the chemical disorder model of DHI-melanin, we solve an equation where a theoretical expression for the ratio of PDCA to PTCA is set to the corresponding experimental value to obtain a plausible Poisson distribution of DHI oligomers. The results demonstrate that the main contributors to DHI-melanin are tetramers and pentamers as shown by the mass spectrometry. PMID:24750564

  17. Plasmid-derived DNA Strand Displacement Gates for Implementing Chemical Reaction Networks

    PubMed Central

    Chen, Yuan-Jyue; Rao, Sundipta D.; Seelig, Georg

    2015-01-01

    DNA nanotechnology requires large amounts of highly pure DNA as an engineering material. Plasmid DNA could meet this need since it is replicated with high fidelity, is readily amplified through bacterial culture and can be stored indefinitely in the form of bacterial glycerol stocks. However, the double-stranded nature of plasmid DNA has so far hindered its efficient use for construction of DNA nanostructures or devices that typically contain single-stranded or branched domains. In recent work, it was found that nicked double stranded DNA (ndsDNA) strand displacement gates could be sourced from plasmid DNA. The following is a protocol that details how these ndsDNA gates can be efficiently encoded in plasmids and can be derived from the plasmids through a small number of enzymatic processing steps. Also given is a protocol for testing ndsDNA gates using fluorescence kinetics measurements. NdsDNA gates can be used to implement arbitrary chemical reaction networks (CRNs) and thus provide a pathway towards the use of the CRN formalism as a prescriptive molecular programming language. To demonstrate this technology, a multi-step reaction cascade with catalytic kinetics is constructed. Further it is shown that plasmid-derived components perform better than identical components assembled from synthetic DNA. PMID:26649734

  18. Iodinated derivatives of vasoactive intestinal peptide (VIP), PHI and PHM: purification, chemical characterization and biological activity

    SciTech Connect

    McMaster, D.; Suzuki, Y.; Rorstad, O.; Lederis, K.

    1987-07-01

    The iodination of vasoactive intestinal peptide (VIP) was studied, using a variety of enzymatic and chemical iodination methods. Reversed phase high performance liquid chromatography (HPLC) was used to purify the reaction products. The lactoperoxidase-glucose oxidase method gave excellent results in terms of reproducibility, iodine incorporation, and yield of the non-oxidized products (Tyr(I)10)VIP and (Tyr(I)22)VIP, and was used to prepare both /sup 125/I and /sup 127/I labelled derivatives. In both cases, direct application to HPLC and a single column system were used. Although the oxidized peptides (Tyr(I)10,Met(O)17)VIP and (Tyr(I)22,Met(O)17)VIP could be generated to varying degrees directly by iodination of VIP, these were most conveniently prepared by iodination of (Met(O)17)VIP. Iodinated derivatives of the homologous peptides PHI and PHM were likewise prepared by rapid, one-step HPLC procedures. The site and degree of iodination were determined by HPLC peptide mapping of tryptic digests and amino acid analyses, and in the case of (Tyr(I)10)VIP also by sequencing. The vasorelaxant activities of the iodinated peptides in bovine cerebral artery preparations did not differ significantly from those of the corresponding noniodinated peptides, with the exception of (Tyr(I)10,Met(O)17)VIP and (Tyr(I)22,Met(O)17)VIP which, unlike (Met(O)17)VIP itself, had slightly lower potency than VIP.

  19. Optimizing Performance Parameters of Chemically-Derived Graphene/p-Si Heterojunction Solar Cell.

    PubMed

    Batra, Kamal; Nayak, Sasmita; Behura, Sanjay K; Jani, Omkar

    2015-07-01

    Chemically-derived graphene have been synthesized by modified Hummers method and reduced using sodium borohydride. To explore the potential for photovoltaic applications, graphene/p-silicon (Si) heterojunction devices were fabricated using a simple and cost effective technique called spin coating. The SEM analysis shows the formation of graphene oxide (GO) flakes which become smooth after reduction. The absence of oxygen containing functional groups, as observed in FT-IR spectra, reveals the reduction of GO, i.e., reduced graphene oxide (rGO). It was further confirmed by Raman analysis, which shows slight reduction in G-band intensity with respect to D-band. Hall effect measurement confirmed n-type nature of rGO. Therefore, an effort has been made to simu- late rGO/p-Si heterojunction device by using the one-dimensional solar cell capacitance software, considering the experimentally derived parameters. The detail analysis of the effects of Si thickness, graphene thickness and temperature on the performance of the device has been presented. PMID:26373050

  20. Poromechanics Parameters of Fluid-Saturated Chemically Active Fibrous Media Derived from a Micromechanical Approach

    PubMed Central

    Parthasarathy, Ranganathan; Singh, Viraj; Spencer, Paulette

    2014-01-01

    The authors have derived macroscale poromechanics parameters for chemically active saturated fibrous media by combining microstructure-based homogenization with Hill's volume averaging. The stress-strain relationship of the dry fibrous media is first obtained by considering the fiber behavior. The constitutive relationships applicable to saturated media are then derived in the poromechanics framework using Hill's Lemmas. The advantage of this approach is that the resultant continuum model assumes a form suited to study porous materials, while retaining the effect of discrete fiber deformation. As a result, the model is able to predict the influence of microscale phenomena such as fiber buckling on the overall behavior, and in particular, on the poromechanics constants. The significance of the approach is demonstrated using the effect of drainage and fiber nonlinearity on monotonic compressive stress-strain behavior. The model predictions conform to the experimental observations for articular cartilage. The method can potentially be extended to other porous materials such as bone, clays, foams, and concrete. PMID:25419475

  1. Role of environmental chemicals, processed food derivatives, and nutrients in the induction of carcinogenesis.

    PubMed

    Persano, Luca; Zagoura, Dimitra; Louisse, Jochem; Pistollato, Francesca

    2015-10-15

    In recent years it has been hypothesized that cancer stem cells (CSCs) are the actual driving force of tumor formation, highlighting the need to specifically target CSCs to successfully eradicate cancer growth and recurrence. Particularly, the deregulation of physiological signaling pathways controlling stem cell proliferation, self-renewal, differentiation, and metabolism is currently considered as one of the leading determinants of cancer formation. Given their peculiar, slow-dividing phenotype and their ability to respond to multiple microenvironmental stimuli, stem cells appear to be more susceptible to genetic and epigenetic carcinogens, possibly undergoing mutations resulting in tumor formation. In particular, some animal-derived bioactive nutrients and metabolites known to affect the hormonal milieu, and also chemicals derived from food processing and cooking, have been described as possible carcinogenic factors. Here, we review most recent literature in this field, highlighting how some environmental toxicants, some specific nutrients and their secondary products can induce carcinogenesis, possibly impacting stem cells and their niches, thus causing tumor growth. PMID:26176180

  2. Chemical nature of implant-derived titanium(IV) ions in synovial fluid

    SciTech Connect

    Silwood, Christopher J.L.; Grootveld, Martin . E-mail: grootvm@lsbu.ac.uk

    2005-05-13

    Previous investigations have indicated a deleterious leakage of Ti(III) and/or Ti(IV) species from Ti-Al-V alloy joint prostheses into adjacent tissue, synovium or synovial fluid (SF) in vivo. In view of the importance of the particular chemical nature of such complexes in determining their biological activity, we have employed high field proton ({sup 1}H) NMR spectroscopy to 'speciate' Ti(IV) in inflammatory SF. Treatment of osteoarthritic SF samples with increasing concentrations of Ti(IV) (0.10-1.03 mM [TiO(C{sub 2}O{sub 4}){sub 2}]{sup 2-}) gave rise to a specific broadening of the citrate proton resonances, indicating that this bioavailable oxygen-donor ligand plays an important role in complexing implant-derived Ti(IV). {sup 1}H NMR analysis of Ti(IV)-loaded SF samples subsequently treated with a large excess of ascorbate (0.05 M) showed that this added Ti(IV) chelator was only poorly effective in removing this metal ion from Ti(IV)-citrate/Ti(IV)-oxycitrate complexes. The results obtained here provide evidence for complexation of the low-molecular-mass (non-protein-bound) fraction of implant-derived Ti(IV) by citrate in vivo.

  3. Chemical looping combustion of biomass-derived syngas using ceria-supported oxygen carriers.

    PubMed

    Huang, H B; Aisyah, L; Ashman, P J; Leung, Y C; Kwong, C W

    2013-07-01

    Cu, Ni and Fe oxides supported on ceria were investigated for their performance as oxygen carriers during the chemical looping combustion of biomass-derived syngas. A complex gas mixture containing CO, H2, CO2, CH4 and other hydrocarbons was used to simulate the complex fuel gas environment derived from biomass gasification. Results show that the transfer of the stored oxygen into oxidants for the supported Cu and Ni oxides at 800°C for the combustion of syngas was effective (>85%). The unsupported Cu oxide showed high oxygen carrying capacity but particle sintering was observed at 800°C. A reaction temperature of 950°C was required for the supported Fe oxides to transfer the stored oxygen into oxidants effectively. Also, for the complex fuel gas environment, the supported Ni oxide was somewhat effective in reforming CH4 and other light hydrocarbons into CO, which may have benefits for the reduction of tar produced during biomass pyrolysis. PMID:23711944

  4. Electrocatalytic processing of renewable biomass-derived compounds for production of chemicals, fuels and electricity

    NASA Astrophysics Data System (ADS)

    Xin, Le

    The dual problems of sustaining the fast growth of human society and preserving the environment for future generations urge us to shift our focus from exploiting fossil oils to researching and developing more affordable, reliable and clean energy sources. Human beings had a long history that depended on meeting our energy demands with plant biomass, and the modern biorefinery technologies realize the effective conversion of biomass to production of transportation fuels, bulk and fine chemicals so to alleviate our reliance on fossil fuel resources of declining supply. With the aim of replacing as much non-renewable carbon from fossil oils with renewable carbon from biomass as possible, innovative R&D activities must strive to enhance the current biorefinery process and secure our energy future. Much of my Ph.D. research effort is centered on the study of electrocatalytic conversion of biomass-derived compounds to produce value-added chemicals, biofuels and electrical energy on model electrocatalysts in AEM/PEM-based continuous flow electrolysis cell and fuel cell reactors. High electricity generation performance was obtained when glycerol or crude glycerol was employed as fuels in AEMFCs. The study on selective electrocatalytic oxidation of glycerol shows an electrode potential-regulated product distribution where tartronate and mesoxalate can be selectively produced with electrode potential switch. This finding then led to the development of AEMFCs with selective production of valuable tartronate or mesoxalate with high selectivity and yield and cogeneration of electricity. Reaction mechanisms of electrocatalytic oxidation of ethylene glycol and 1,2-propanediol were further elucidated by means of an on-line sample collection technique and DFT modeling. Besides electro-oxidation of biorenewable alcohols to chemicals and electricity, electrocatalytic reduction of keto acids (e.g. levulinic acid) was also studied for upgrading biomass-based feedstock to biofuels while achieving renewable electricity storage. Meanwhile, ORR that is often coupled in AEMFCs on the cathode was investigated on non-PGM electrocatalyst with comparable activity to commercial Pt/C. The electro-biorefinery process could be coupled with traditional biorefinery operation and will play a significant role in our energy and chemical landscape.

  5. Chemical synthesis and formulation design of a PEGylated vasoactive intestinal peptide derivative with improved metabolic stability.

    PubMed

    Onoue, Satomi; Matsui, Takuya; Kato, Masashi; Mizumoto, Takahiro; Liu, Baosheng; Liu, Liang; Karaki, Shin-ichiro; Kuwahara, Atsukazu; Yamada, Shizuo

    2013-06-14

    The present study aimed to design a PEGylated VIP derivative, [Arg(15, 20, 21), Leu(17)]-VIP-GRR (IK312532), with improved metabolic stability, and develop its respirable powder (RP) formulation for inhalation therapy. IK312532 was chemically conjugated with PEG (5 kDa, P5K), the physicochemical and biochemical properties of which were characterized by CD spectral analysis, binding assays, and metabolic stability. CD spectral analysis demonstrated that PEG conjugation had no impact on the conformational structure of IK312532. Although the receptor-binding activity of IK312532/P5K (IC??: 82 nM) was estimated to be ca. 30-fold less than that of IK312532 (IC??: 2.8 nM), the metabolic stability of IK312532/P5K was highly improved. The IK312532/P5K was jet-milled and blended with lactose carrier particles to provide RP formulation of IK312532/P5K (IK312532/P5K-RP). In vitro inhalation performance and in vivo pharmacological effects of the IK312532/P5K-RP in antigen-sensitized rats were also evaluated. In cascade impactor analyses, fine particle fraction of IK312532/P5K-RP was calculated to be ca. 37%. Insufflation of IK312532/P5K-RP (150 ?g of IK312532/P5K) in antigen-sensitized rats resulted in marked attenuation of inflammatory events, as evidenced by significant decreases in inflammatory biomarkers and granulocyte recruitment in pulmonary tissue 24h after the antigen challenge. From these findings, PEGylation of a VIP derivative, as well as its strategic application to the RP formulation, may be a viable approach to improve its therapeutic potential for the treatment of airway inflammatory diseases. PMID:23608612

  6. Correlation of in Vitro Cytokine Responses with the Chemical Composition of Soil-Derived Particulate Matter

    PubMed Central

    Veranth, John M.; Moss, Tyler A.; Chow, Judith C.; Labban, Raed; Nichols, William K.; Walton, John C.; Watson, John G.; Yost, Garold S.

    2006-01-01

    We treated human lung epithelial cells, type BEAS-2B, with 10–80 μg/cm2 of dust from soils and road surfaces in the western United States that contained particulate matter (PM) < 2.5 μm aerodynamic diameter. Cell viability and cytokine secretion responses were measured at 24 hr. Each dust sample is a complex mixture containing particles from different minerals mixed with biogenic and anthropogenic materials. We determined the particle chemical composition using methods based on the U.S. Environmental Protection Agency Speciation Trends Network (STN) and the National Park Service Interagency Monitoring of Protected Visual Environments (IMPROVE) network. The functionally defined carbon fractions reported by the ambient monitoring networks have not been widely used for toxicology studies. The soil-derived PM2.5 from different sites showed a wide range of potency for inducing the release of the proinflammatory cytokines interleukin-6 (IL-6) and IL-8 in vitro. Univariate regression and multivariate redundancy analysis were used to test for correlation of viability and cytokine release with the concentrations of 40 elements, 7 ions, and 8 carbon fractions. The particles showed positive correlation between IL-6 release and the elemental and pyrolyzable carbon fractions, and the strongest correlation involving crustal elements was between IL-6 release and the aluminum:silicon ratio. The observed correlations between low-volatility organic components of soil- and road-derived dusts and the cytokine release by BEAS-2B cells are relevant for investigation of mechanisms linking specific air pollution particle types with the initiating events leading to airway inflammation in sensitive populations. PMID:16507455

  7. Chemical Solution Derived Planarization Layers for Highly Aligned IBAD MgO Templates

    SciTech Connect

    Paranthaman, Mariappan Parans; Aytug, Tolga; Stan, Liliana; Jia, Quanxi; Cantoni, Claudia; Wee, Sung Hun

    2014-01-01

    The main goal of this research is to develop a chemical solution derived planarization layer to fabricate highly aligned IBAD-MgO templates for the development of high temperature superconductor (HTS) based coated conductors. The standard IBAD-MgO template needs an additional electrochemical polishing step of the mechanically polished 50- m-thick Hastelloy C-276 substrates to ensure a flat and smooth surface for subsequent growth of multi-layer buffer architectures, which include: sputtered 80-nm Al2O3; sputtered 7-nm Y2O3; IBAD 10-nm MgO; sputtered 30-nm homo-epi MgO; and sputtered 30-nm LaMnO3 (LMO) layers. We have successfully developed a solution planarization layer that removes the electrochemical polishing step and also acts as a barrier layer. Crack-free, smooth Al2O3 layers were prepared on mechanically polished Hastelloy substrates using a chemical solution process. A nearly 10-15-nm thick Al2O3 layer was formed with each coating and the coating was repeated several times to achieve the desired film thickness with intermediate heat-treatments after each coating. The Al2O3 planarization layer significantly reduced the surface roughness of the substrate. The average surface roughness value, Ra for a starting substrate was 9-10 nm. After 8 coatings of Al2O3 layer, the Ra was reduced to 2 nm. Highly aligned IBAD-MgO layers with out-of-plane and in-plane textures comparable to the standard IBAD-MgO layers were successfully deposited on top of the solution planarization Al2O3 layers with an Y2O3 nucleation layer using a reel-to-reel ion-beam sputtering system. Both homo-epi MgO and LMO layers were subsequently deposited on the IBAD-MgO layers using rf sputtering to complete the buffer stack required for the growth of HTS films. YBa2Cu3O7- (YBCO) films with a thickness of 0.8 m deposited on these IBAD-MgO templates by pulsed laser deposition showed a high self-field critical current density, Jc of 3.04 MA/cm2 at 77 K and 6.05 MA/cm2 at 65 K. These results demonstrate that a low-cost chemical-solution-based, high-throughput Al2O3 planarization layer can remove the electro-polishing step and replace sputtered Al2O3 layers for the production of high Jc YBCO-coated conductors.

  8. Catalytic conversion of biomass pyrolysis-derived compounds with chemical liquid deposition (CLD) modified ZSM-5.

    PubMed

    Zhang, Huiyan; Luo, Mengmeng; Xiao, Rui; Shao, Shanshan; Jin, Baosheng; Xiao, Guomin; Zhao, Ming; Liang, Junyu

    2014-03-01

    Chemical liquid deposition (CLD) with KH550, TEOS and methyl silicone oil as the modifiers was used to modify ZSM-5 and deposit its external acid sites. The characteristics of modified catalysts were tested by catalytic conversion of biomass pyrolysis-derived compounds. The effects of different modifying conditions (deposited amount, temperature, and time) on the product yields and selectivities were investigated. The results show KH550 modified ZSM-5 (deposited amount of 4%, temperature of 20°C and time of 6h) produced the maximum yields of aromatics (24.5%) and olefins (16.5%), which are much higher than that obtained with original ZSM-5 catalyst (18.8% aromatics and 9.8% olefins). The coke yield decreased from 44.1% with original ZSM-5 to 26.7% with KH550 modified ZSM-5. The selectivities of low-molecule-weight hydrocarbons (ethylene and benzene) decreased, while that of higher molecule-weight hydrocarbons (propylene, butylene, toluene, and naphthalene) increased comparing with original ZSM-5. PMID:24413482

  9. Chemical Characterization of Beer Aging Products Derived from Hard Resin Components in Hops (Humulus lupulus L.).

    PubMed

    Taniguchi, Yoshimasa; Yamada, Makiko; Taniguchi, Harumi; Matsukura, Yasuko; Shindo, Kazutoshi

    2015-11-25

    The bitter taste of beer originates from resins in hops (Humulus lupulus L.), which are classified into two subtypes (soft and hard). Whereas the nature and reactivity of soft-resin-derived compounds, such as α-, β-, and iso-α-acids, are well studied, there is only a little information on the compounds in hard resin. For this work, hard resin was prepared from stored hops and investigated for its compositional changes in an experimental model of beer aging. The hard resin contained a series of α-acid oxides. Among them, 4'-hydroxyallohumulinones were unstable under beer storage conditions, and their transformation induced primary compositional changes of the hard resin during beer aging. The chemical structures of the products, including novel polycyclic compounds scorpiohumulinols A and B and dicyclohumulinols A and B, were determined by HRMS and NMR analyses. These compounds were proposed to be produced via proton-catalyzed cyclization reactions of 4'-hydroxyallohumulinones. Furthermore, they were more stable than their precursor 4'-hydroxyallohumulinones during prolonged storage periods. PMID:26507444

  10. Surface studies of aminoferrocene derivatives on gold: electrochemical sensors for chemical warfare agents.

    PubMed

    Khan, Mohammad A K; Long, Yi-Tao; Schatte, Gabriele; Kraatz, Heinz-Bernhard

    2007-04-01

    The cystamine conjugate [(BocNH)Fc(CO)CSA]2 was prepared by coupling cystamine with the N-protected ferrocene amino acid derivative BocHN-Fc-COOH and was fully characterized by spectroscopic methods and by single-crystal X-ray diffraction. The cystamine conjugate forms films on gold substrates, which upon deprotection of the amino group, react with chemical warfare agent (CWA) mimics, upon which the redox properties of the Fc group are affected significantly. Cyclic voltammetry shows 50(5) mV anodic shifts of the Fc redox potentials after exposure to EtSCH2CH2Cl, a simulant for sulfur mustard HD (MA), and (NC)(EtO)2P(O), a simulant for nerve agent Tabun (NA). Exposure to MA and NA causes an increase in 2.3 and 4.5 ng mass, respectively, in QCM which indicates ca. 70% efficiency in Boc-deprotection. Ellipsometry measured a film thickness increase from 6(+/-1) A for the deprotected film to 10(+/-4) A for the film modified with MA and to 7(+/-2) A for the film modified with NA. AFM measurements show changes in the thickness and morphology of the film after reaction with MA and NA. The surfaces were analyzed by X-ray photoelectron spectroscopy (XPS) and clearly show the attachment of the cystamine conjugate on the surface and its reaction with CWA mimics. PMID:17319647

  11. Antioxidant capacity and chemical profiles of Satureja montana L. Honey: hotrienol and syringyl derivatives as biomarkers.

    PubMed

    Jerković, Igor; Tuberoso, Carlo I G; Marijanović, Zvonimir; Kranjac, Marina; Malenica-Staver, M

    2015-07-01

    The present study is focused on the antioxidant capacity and chemical profiling of eight Croatian Satureja montana L. honey samples. Among the 20 compounds obtained by headspace solid-phase microextraction (HS-SPME) and identified by GC-FID and GC/MS analyses, hotrienol was predominant (75.9-81.7%). The honey matrix volatile/semivolatile profile was investigated by ultrasonic solvent extraction (USE) followed by GC-FID and GC/MS analyses. The major compounds identified by this latter method were the sinapic-acid derivatives methyl syringate (36.2-72.8%) and syringaldehyde (2.2-43.1%). Direct, targeted HPLC-DAD analyses of the native honey samples revealed the presence of methyl syringate (7.10-39.60 mg/kg) and syringic acid (0.10-1.70 mg/kg). In addition, the total phenolic content of the samples was determined by the FolinCiocalteu assay (311.0-465.9 mg GAE/kg), and the antioxidant capacity was evaluated by the DPPH radical-scavenging activity (0.5-1.0 mmol TEAC/kg) and the ferric reducing antioxidant power (2.5-5.1 mmol Fe(2+) /kg). PMID:26172325

  12. Chemical Compositional, Biological, and Safety Studies of a Novel Maple Syrup Derived Extract for Nutraceutical Applications

    PubMed Central

    2015-01-01

    Maple syrup has nutraceutical potential given the macronutrients (carbohydrates, primarily sucrose), micronutrients (minerals and vitamins), and phytochemicals (primarily phenolics) found in this natural sweetener. We conducted compositional (ash, fiber, carbohydrates, minerals, amino acids, organic acids, vitamins, phytochemicals), in vitro biological, and in vivo safety (animal toxicity) studies on maple syrup extracts (MSX-1 and MSX-2) derived from two declassified maple syrup samples. Along with macronutrient and micronutrient quantification, thirty-three phytochemicals were identified (by HPLC-DAD), and nine phytochemicals, including two new compounds, were isolated and identified (by NMR) from MSX. At doses of up to 1000 mg/kg/day, MSX was well tolerated with no signs of overt toxicity in rats. MSX showed antioxidant (2,2-diphenyl-1-picrylhydrazyl (DPPH) assay) and anti-inflammatory (in RAW 264.7 macrophages) effects and inhibited glucose consumption (by HepG2 cells) in vitro. Thus, MSX should be further investigated for potential nutraceutical applications given its similarity in chemical composition to pure maple syrup. PMID:24983789

  13. Chemically modified, non-anticoagulant heparin derivatives are potent galectin-3 binding inhibitors and inhibit circulating galectin-3-promoted metastasis

    PubMed Central

    Sindrewicz, Paulina; Hughes, Ashley J.; French, Neil S.; Lian, Lu-Yun; Yates, Edwin A.; Pritchard, D. Mark; Rhodes, Jonathan M.; Turnbull, Jeremy E.; Yu, Lu-Gang

    2015-01-01

    Concentrations of circulating galectin-3, a metastasis promoter, are greatly increased in cancer patients. Here we show that 2- or 6-de-O-sulfated, N-acetylated heparin derivatives are galectin-3 binding inhibitors. These chemically modified heparin derivatives inhibited galectin-3-ligand binding and abolished galectin-3-mediated cancer cell-endothelial adhesion and angiogenesis. Unlike standard heparin, these modified heparin derivatives and their ultra-low molecular weight sub-fractions had neither anticoagulant activity nor effects on E-, L- or P-selectin binding to their ligands nor detectable cytotoxicity. Intravenous injection of such heparin derivatives (with cancer cells pre-treated with galectin-3 followed by 3 subcutaneous injections of the derivatives) abolished the circulating galectin-3-mediated increase in lung metastasis of human melanoma and colon cancer cells in nude mice. Structural analysis using nuclear magnetic resonance and synchrotron radiation circular dichroism spectroscopies showed that the modified heparin derivatives bind to the galectin-3 carbohydrate-recognition domain. Thus, these chemically modified, non-anticoagulant, low-sulfated heparin derivatives are potent galectin-3 binding inhibitors with substantial potential as anti-metastasis/cancer drugs. PMID:26160844

  14. Chemically and biologically-mediated fertilizing value of manure-derived biochar.

    PubMed

    Subedi, R; Taupe, N; Ikoyi, I; Bertora, C; Zavattaro, L; Schmalenberger, A; Leahy, J J; Grignani, C

    2016-04-15

    This study evaluates the potential of manure-derived biochars in promoting plant growth and enhancing soil chemical and biological properties during a 150day pot experiment. Biochars from pyrolysis of poultry litter (PL) and swine manure (SM) at 400 and 600°C, and a commonly available wood chip (WC) biochar produced at high temperature (1000°C) were incorporated to silt-loam (SL) and sandy (SY) soils on a 2% dry soil weight basis. Ryegrass was sown and moisture was adjusted to 60% water filled pore space (WFPS). The PL400 and SM400 biochars significantly increased (p<0.05) shoot dry matter (DM) yields (SL soil) and enhanced nitrogen (N), phosphorus (P) and potassium (K) uptake by the plants in both soils, compared to the Control. All biochars significantly increased the soil carbon (C) contents compared to the Control. Total N contents were significantly greater for PL400 and PL600 treatments in both soils. The dehydrogenase activity (DA) significantly increased for PL400 and SM400 treatments and was positively correlated with the volatile matter (VM) contents of the biochars, while β-glucosidase activity (GA) decreased for the same treatments in both soils. All biochars significantly shifted (p≤0.05) the bacterial community structure compared to the Control. This study suggests that pyrolysis of animal manures can produce a biochar that acts as both soil amendment and an organic fertilizer as proven by increased NPK uptake, positive liming effect and high soil nutrient availability, while WC biochar could work only in combination with fertilizers (organic as well as mineral). PMID:26851878

  15. Chemically Defined and Xeno-Free Cryopreservation of Human Adipose-Derived Stem Cells

    PubMed Central

    López, Melany; Bollag, Roni J.; Yu, Jack C.; Isales, Carlos M.; Eroglu, Ali

    2016-01-01

    The stromal compartment of adipose tissue harbors multipotent cells known as adipose-derived stem cells (ASCs). These cells can differentiate into various lineages including osteogenic, chrondrogenic, adipogenic, and neurogenic; this cellular fraction may be easily obtained in large quantities through a clinically safe liposuction procedure. Therefore, ASCs offer exceptional opportunities for tissue engineering and regenerative medicine. However, current practices involving ASCs typically use fetal bovine serum (FBS)-based cryopreservation solutions that are associated with risks of immunological reactions and of transmitting infectious diseases and prions. To realize clinical applications of ASCs, serum- and xeno-free defined cryopreservation methods are needed. To this end, an animal product-free chemically defined cryopreservation medium was formulated by adding two antioxidants (reduced glutathione and ascorbic acid 2-phosphate), two polymers (PVA and ficoll), two permeating cryoprotectants (ethylene glycol and dimethylsulfoxide), a disaccharide (trehalose), and a calcium chelator (EGTA) to HEPES-buffered DMEM/F12. To limit the number of experimental groups, the concentration of trehalose, both polymers, and EGTA was fixed while the presence of the permeating CPAs and antioxidants was varied. ASCs suspended either in different versions of the defined medium or in the conventional undefined cryopreservation medium (10% dimethylsulfoxide+10% DMEM/F12+80% serum) were cooled to -70°C at 1°C/min before being plunged into liquid nitrogen. Samples were thawed either in air or in a water bath at 37°C. The presence of antioxidants along with 3.5% concentration of each penetrating cryoprotectant improved the freezing outcome to the level of the undefined cryopreservation medium, but the plating efficiency was still lower than that of unfrozen controls. Subsequently, increasing the concentration of both permeating cryoprotectants to 5% further improved the plating efficiency to the level of unfrozen controls. Moreover, ASCs cryopreserved in this defined medium retained their multipotency and chromosomal normality. These results are of significance for tissue engineering and clinical applications of stem cells. PMID:27010403

  16. Overview of data and conceptual approaches for derivation of quantitative structure-activity relationships for ecotoxicological effects of organic chemicals.

    PubMed

    Bradbury, Steven P; Russom, Christine L; Ankley, Gerald T; Schultz, T Wayne; Walker, John D

    2003-08-01

    The use of quantitative structure-activity relationships (QSARs) in assessing potential toxic effects of organic chemicals on aquatic organisms continues to evolve as computational efficiency and toxicological understanding advance. With the ever-increasing production of new chemicals, and the need to optimize resources to assess thousands of existing chemicals in commerce, regulatory agencies have turned to QSARs as essential tools to help prioritize tiered risk assessments when empirical data are not available to evaluate toxicological effects. Progress in designing scientifically credible QSARs is intimately associated with the development of empirically derived databases of well-defined and quantified toxicity endpoints, which are based on a strategic evaluation of diverse sets of chemical structures, modes of toxic action, and species. This review provides a brief overview of four databases created for the purpose of developing QSARs for estimating toxicity of chemicals to aquatic organisms. The evolution of QSARs based initially on general chemical classification schemes, to models founded on modes of toxic action that range from nonspecific partitioning into hydrophobic cellular membranes to receptor-mediated mechanisms is summarized. Finally, an overview of expert systems that integrate chemical-specific mode of action classification and associated QSAR selection for estimating potential toxicological effects of organic chemicals is presented. PMID:12924578

  17. Chemical derivation to enhance the chemical/oxidative stability of resorcinol-formaldehyde (R-F) resin

    SciTech Connect

    Hubler, T.L.; Shaw, W.J.; Brown, G.N.; Linehan, J.C.; Franz, J.A.; Hart, T.R.; Hogan, M.O.

    1996-09-01

    Tank wastes at Hanford and SRS contain highly alkaline supernate solutions of conc. Na, K nitrates with large amounts of {sup 137}Cs. It is desirable to remove and concentrate the highly radioactive fraction for vitrification. One candidate ion exchange material for removing the radiocesium is R-F resin. This report summarizes studies into synthesis and characterization of 4-derivatized R-F resins prepared in pursuit of more chemically/oxidatively robust resin. 85% 4-fluororesorcinol/15% phenol formaldehyde resin appears to have good stability in alkaline solution, although there may be some nucleophilic displacement reaction during synthesis; further studies are needed.

  18. Characterization of high-k HfO2 films prepared using chemically modified alkoxy-derived solutions

    NASA Astrophysics Data System (ADS)

    Suzuki, Kazuyuki; Kato, Kazumi

    2009-03-01

    The HfO2 films were prepared using alkoxy-derived precursor solutions. The effects of the chemical composition of precursor solutions on the microstructure development and electrical properties were investigated. The flatness and refractive index of the HfO2 films were improved by using diethanolamine-added solution. This result is considered to be due to the difference in the progress of organic decomposition and the behavior of nucleation and grain growth. The difference in the chemical composition affected the electrical properties such as leakage current and capacitance-voltage characteristics, which are related to the defects in the film and interface state.

  19. Mass production of chemicals from biomass-derived oil by directly atmospheric distillation coupled with co-pyrolysis

    PubMed Central

    Zhang, Xue-Song; Yang, Guang-Xi; Jiang, Hong; Liu, Wu-Jun; Ding, Hong-Sheng

    2013-01-01

    Production of renewable commodity chemicals from bio-oil derived from fast pyrolysis of biomass has received considerable interests, but hindered by the presence of innumerable components in bio-oil. In present work, we proposed and experimentally demonstrated an innovative approach combining atmospheric distillation of bio-oil with co-pyrolysis for mass production of renewable chemicals from biomass, in which no waste was produced. It was estimated that 51.86 wt.% of distillate just containing dozens of separable organic components could be recovered using this approach. Ten protogenetic and three epigenetic compounds in distillate were qualitatively identified by gas chromatography/mass spectrometry and quantified by gas chromatography. Among them, the recovery efficiencies of acetic acid, propanoic acid, and furfural were all higher than 80 wt.%. Formation pathways of the distillate components in this process were explored. This work opens up a fascinating prospect for mass production of chemical feedstock from waste biomass. PMID:23350028

  20. Nanochemistry-derived Bi2WO6 nanostructures: towards production of sustainable chemicals and fuels induced by visible light.

    PubMed

    Zhang, Nan; Ciriminna, Rosaria; Pagliaro, Mario; Xu, Yi-Jun

    2014-08-01

    Low cost and easily made bismuth tungstate (Bi2WO6) could be one of the key technologies to make chemicals and fuels from biomass, atmospheric carbon dioxide and water at low cost using solar radiation as an energy source. Its narrow band gap (2.8 eV) enables ideal visible light (λ > 400 nm) absorption. Yet, it is the material's shape, namely the superstructure morphology wisely created via a nanochemistry approach, which leads to better electron-hole separation and much higher photoactivity. Recent results coupled to the versatile photochemistry of this readily available semiconductor suggest that the practical application of nanochemistry-derived Bi2WO6 nanostructures for the synthesis of value-added fine chemicals and fuel production is possible. We describe progress in this important field of chemical research from a nanochemistry viewpoint, and identify opportunities for further progress. PMID:24776966

  1. Mass production of chemicals from biomass-derived oil by directly atmospheric distillation coupled with co-pyrolysis

    NASA Astrophysics Data System (ADS)

    Zhang, Xue-Song; Yang, Guang-Xi; Jiang, Hong; Liu, Wu-Jun; Ding, Hong-Sheng

    2013-01-01

    Production of renewable commodity chemicals from bio-oil derived from fast pyrolysis of biomass has received considerable interests, but hindered by the presence of innumerable components in bio-oil. In present work, we proposed and experimentally demonstrated an innovative approach combining atmospheric distillation of bio-oil with co-pyrolysis for mass production of renewable chemicals from biomass, in which no waste was produced. It was estimated that 51.86 wt.% of distillate just containing dozens of separable organic components could be recovered using this approach. Ten protogenetic and three epigenetic compounds in distillate were qualitatively identified by gas chromatography/mass spectrometry and quantified by gas chromatography. Among them, the recovery efficiencies of acetic acid, propanoic acid, and furfural were all higher than 80 wt.%. Formation pathways of the distillate components in this process were explored. This work opens up a fascinating prospect for mass production of chemical feedstock from waste biomass.

  2. Disruption of BASIGIN decreases lactic acid export and sensitizes non-small cell lung cancer to biguanides independently of the LKB1 status.

    PubMed

    Granja, Sara; Marchiq, Ibtissam; Le Floch, Renaud; Moura, Conceição Souto; Baltazar, Fátima; Pouysségur, Jacques

    2015-03-30

    Most cancers rely on aerobic glycolysis to generate energy and metabolic intermediates. To maintain a high glycolytic rate, cells must efficiently export lactic acid through the proton-coupled monocarboxylate transporters (MCT1/4). These transporters require a chaperone, CD147/BASIGIN (BSG) for trafficking to the plasma membrane and function.To validate the key role of these transporters in lung cancer, we first analysed the expression of MCT1/4 and BSG in 50 non-small lung cancer (NSCLC) cases. These proteins were specifically upregulated in tumour tissues. We then disrupted BSG in three NSCLC cell lines (A549, H1975 and H292) via 'Zinc-Finger Nucleases'. The three homozygous BSG-/- cell lines displayed a low MCT activity (10- to 5-fold reduction, for MCT1 and MCT4, respectively) compared to wild-type cells. Consequently, the rate of glycolysis, compared to the wild-type counterpart, was reduced by 2.0- to 3.5-fold, whereas the rate of respiration was stimulated in BSG-/- cell lines. Both wild-type and BSG-null cells were extremely sensitive to the mitochondria inhibitor metformin/phenformin in normoxia. However, only BSG-null cells, independently of their LKB1 status, remained sensitive to biguanides in hypoxia in vitro and tumour growth in nude mice. Our results demonstrate that inhibiting glycolysis by targeting lactic acid export sensitizes NSCLC to phenformin. PMID:25894929

  3. Quantum chemical calculations to reveal the relationship between the chemical structure and the fluorescence characteristics of phenylquinolinylethynes and phenylisoquinolinylethynes derivatives, and to predict their relative fluorescence intensity.

    PubMed

    Riahi, Siavash; Beheshti, Abolghasem; Ganjali, Mohammad Reza; Norouzi, Parviz

    2009-12-01

    In this paper the relationship between the chemical structure and fluorescence characteristics of 30 phenylquinolinylethyne (PhQE), and phenylisoquinolinylethyne (PhIE) derivatives compounds employing ab initio calculations have been elucidated. Quantum chemical calculations (6-31G) were carried out to obtain: the optimized geometry, energy levels, charges and dipole moments of these compounds, in the singlet (steady and excited states) and triplet states. The relationship between quantum chemical descriptors, and wavelength of maximum excitation and emission indicated that these two parameters have the most correlation with quantum chemical hardness (eta). Also, stokes shift has the most correlation with the square of difference between the maximum of positive charges in the singlet steady and singlet excited states. The quantitative structure-property relationship (QSPR) of PhQE and PhIE was studied for relative fluorescence intensity (RFI). The genetic algorithm (GA) was applied to select the variables that resulted in the best-fit models. After the variable selection, multiple linear regression (MLR) and support vector machine (SVM) were both utilized to construct linear and non-linear QSPR models, respectively. The SVM model demonstrated a better performance than that of the MLR model. The route mean square error (RMSE) in the training and the test sets for the SVM model was 0.195 and 0.324, and the correlation coefficients were 0.965 and 0.960, respectively, thus revealing the reliability of this model. The resulting data indicated that SVM could be used as a powerful modeling tool for QSPR studies. According to the best of our knowledge, this is the first research on QSPR studies to predict RFI for a series of PhQE and PhIE derivative compounds using SVM. PMID:19854100

  4. Atmospheric Chemical Transport Based on High Resolution Model- Derived Winds: A Case Study

    NASA Technical Reports Server (NTRS)

    Hannan, John R.; Fuelberg, Henry E.; Thompson, Anne M.; Bieberbach, George, Jr.; Knabb, Richard D.; Kondo, Yutaka; Anderson, Bruce E.; Browell, Edward V.; Gregory, Gerald L.; Sachse, Glen; Singh, Hanwant B.

    1999-01-01

    Flight 10 of NASA's Subsonic Assessment (SASS) Ozone and Nitrogen Oxide Experiment (SONEX) extended southwest of Lajes, Azores. A variety of chemical signatures were encountered. These signatures are examined in detail, relating them to meteorological data from a high resolution numerical model having horizontal grid spacing of 30 and 90 km and 26 vertical levels. The meteorological output at hourly intervals is used to create backward trajectories from the locations of the chemical signatures. Four major categories of chemical signatures are discussed-stratospheric, lightning, continental pollution, and a transition layer. The strong stratospheric signal is encountered just south of the Azores in a region of depressed tropopause height. Three chemical signatures at different altitudes in the upper troposphere are attributed to lightning. Backward trajectories arriving at locations of these signatures are related to locations of cloud-to-ground lightning. Results show that the trajectories pass through regions of lightning 1-2 days earlier over the eastern Gulf of Mexico and off the southeast coast of the United States. The lowest leg of the flight exhibits a chemical signature consistent with continental pollution. Trajectories arriving at this signature are found to pass over the highly populated Northeast Corridor of the United States. Surface based pollution apparently is lofted to the altitudes of the trajectories by convective clouds along the East Coast that did not contain lightning. Finally, a chemical transition layer is described. Its chemical signature is intermediate to those of lightning and continental pollution. Trajectories arriving in this layer pass between the trajectories of the lightning and pollution signatures. Thus, they probably are impacted by both sources.

  5. Chemical investigation of commercial grape seed derived products to assess quality and detect adulteration.

    PubMed

    Villani, Tom S; Reichert, William; Ferruzzi, Mario G; Pasinetti, Giulio M; Simon, James E; Wu, Qingli

    2015-03-01

    Fundamental concerns in quality control arise due to increasing use of grape seed extract (GSE) and the complex chemical composition of GSE. Proanthocyanidin monomers and oligomers are the major bioactive compounds in GSE. Given no standardized criteria for quality, large variation exists in the composition of commercial GSE supplements. Using HPLC/UV/MS, 21 commercial GSE containing products were purchased and chemically profiled, major compounds quantitated, and compared against authenticated grape seed extract, peanut skin extract, and pine bark extract. The antioxidant capacity and total polyphenol content for each sample was also determined and compared using standard techniques. Nine products were adulterated, found to contain peanut skin extract. A wide degree of variability in chemical composition was detected in commercial products, demonstrating the need for development of quality control standards for GSE. A TLC method was developed to allow for rapid and inexpensive detection of adulteration in GSE by peanut skin. PMID:25306345

  6. Chemical Synthesis and Biological Activities of Novel Pleuromutilin Derivatives with Substituted Amino Moiety

    PubMed Central

    Shang, Ruofeng; Wang, Shengyu; Xu, Ximing; Yi, Yunpeng; Guo, Wenzhu; YuLiu; Liang, Jianping

    2013-01-01

    Novel pleuromutilin derivatives designed based on the structure of valnemulin were synthesized and evaluated for their in vitro antibacterial activities. These pleuromutilin derivatives with substituted amino moiety exhibited excellent activities against methicillin-resistant Staphylococcus aureus, methicillin-resistant Staphylococcus epidermidis, Escherichia coli, and Streptococcus agalactiae. Compound 5b showed the highest antibacterial activities and even exceeded tiamulin. Moreover, the docking experiments provided information about the binding model between the synthesized compounds and peptidyl transferase center (PTC) of 23S rRNA. PMID:24376551

  7. Chemical synthesis and biological activities of novel pleuromutilin derivatives with substituted amino moiety.

    PubMed

    Shang, Ruofeng; Wang, Shengyu; Xu, Ximing; Yi, Yunpeng; Guo, Wenzhu; Yuliu; Liang, Jianping

    2013-01-01

    Novel pleuromutilin derivatives designed based on the structure of valnemulin were synthesized and evaluated for their in vitro antibacterial activities. These pleuromutilin derivatives with substituted amino moiety exhibited excellent activities against methicillin-resistant Staphylococcus aureus, methicillin-resistant Staphylococcus epidermidis, Escherichia coli, and Streptococcus agalactiae. Compound 5b showed the highest antibacterial activities and even exceeded tiamulin. Moreover, the docking experiments provided information about the binding model between the synthesized compounds and peptidyl transferase center (PTC) of 23S rRNA. PMID:24376551

  8. Influence of pecan-derived biochar on chemical properties of a Norfolk loamy sand soil

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Sandy, Coastal Plain soils in the Southeastern USA are low (0.3 to 2%) in soil organic carbon contents (SOC) due to high soil temperatures, abundant rainfall, and a low physico-chemical protection of organic substances. Consequently, the soils have poor soil fertility characteristics. A strategy to ...

  9. Biogas upgrading by chemical absorption using ammonia rich absorbents derived from wastewater.

    PubMed

    McLeod, Andrew; Jefferson, Bruce; McAdam, Ewan J

    2014-12-15

    The use of ammonia (NH3) rich wastewaters as an ecological chemical absorption solvent for the selective extraction of carbon dioxide (CO2) during biogas upgrading to 'biomethane' has been studied. Aqueous ammonia absorbents of up to 10,000 gNH3 m(-3) demonstrated CO2 absorption rates higher than recorded in the literature for packed columns using 20,000-80,000 g NH3 m(-3) which can be ascribed to the process intensification provided by the hollow fibre membrane contactor used in this study to support absorption. Centrifuge return liquors (2325 g m(-3) ionised ammonium, NH4(+)) and a regenerant (477 gNH4(+) m(-3)) produced from a cationic ion exchanger used to harvest NH4(+) from crude wastewater were also tested. Carbon dioxide fluxes measured for both wastewaters compared reasonably with analogue ammonia absorption solvents of equivalent NH3 concentration. Importantly, this demonstrates that ammonia rich wastewaters can facilitate chemically enhanced CO2 separation which eliminates the need for costly exogenic chemicals or complex chemical handling which are critical barriers to implementation of chemical absorption. When testing NH3 analogues, the potential to recover the reaction product ammonium bicarbonate (NH4HCO3) in crystalline form was also illustrated. This is significant as it suggests a new pathway for ammonia separation which avoids biological nitrification and produces ammonia stabilised into a commercially viable fertiliser (NH4HCO3). However, in real ammonia rich wastewaters, sodium bicarbonate and calcium carbonate were preferentially formed over NH4HCO3 although it is proposed that NH4HCO3 can be preferentially formed by manipulating both ion exchange and absorbent chemistry. PMID:25277752

  10. Chemicals derived from pyrolysis bio-oils as antioxidants in fuels and lubricants

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Softwood and hardwood lignins and hardwood were pyrolyzed to produce bio-oils to produce lignin-derived bio-oils of which phenols were the major component. These bio-oils were extracted with alkali to yield a range of lignin-related phenols having molecular weights (MWs) from 110 to 344. When tested...

  11. Identification of human-derived volatile chemicals that interfere with attraction of Aedes aegypti mosquitoes.

    PubMed

    Logan, James G; Birkett, Michael A; Clark, Suzanne J; Powers, Stephen; Seal, Nicola J; Wadhams, Lester J; Mordue Luntz, A Jennifer; Pickett, John A

    2008-03-01

    It is known that human individuals show different levels of attractiveness to mosquitoes. In this study, we investigated the chemical basis for low attractiveness. We recorded behaviors of Aedes aegypti toward the hands of human volunteers and toward the volatile chemicals produced by their bodies. Some individuals, and their corresponding volatiles, elicited low upwind flight, relative attraction, and probing activity. Analyzing the components by gas chromatography coupled to electrophysiological recordings from the antennae of Aedes aegypti, enabled the location of 33 physiologically relevant compounds. The results indicated that higher levels of specific compounds may be responsible for decreased "attractiveness." In behavioral experiments, five of the compounds caused a significant reduction in upwind flight of Aedes aegypti to attractive human hands. Thus, unattractiveness of individuals may result from a repellent, or attractant "masking," mechanism. PMID:18306972

  12. Electron impact and chemical ionization mass spectral analysis of a volatile uranyl derivative

    SciTech Connect

    Reutter, D.J.; Hardy, D.R.

    1981-01-01

    Quadrupole mass spectral analysis of the volatile uranium ligand complex bis (1,1,1,5,5,5-hexafluoro-2,4-pentanedionato) dioxouranium-di-n-butyl sulfoxide is described utilizing electron impact (EI) and methane chemical ionization (CI) ion sources. All major ions are tentatively identified and the potential usefulness of this complex for determining uranium isotope /sup 235/U//sup 238/U abundance is demonstrated.

  13. Protein Structural Information Derived from NMR Chemical Shift with the Neural Network Program TALOS-N

    PubMed Central

    Shen, Yang; Bax, Ad

    2015-01-01

    Summary Chemical shifts are obtained at the first stage of any protein structural study by NMR spectroscopy. Chemical shifts are known to be impacted by a wide range of structural factors and the artificial neural network based TALOS-N program has been trained to extract backbone and sidechain torsion angles from 1H, 15N and 13C shifts. The program is quite robust, and typically yields backbone torsion angles for more than 90% of the residues, and sidechain χ1 rotamer information for about half of these, in addition to reliably predicting secondary structure. The use of TALOS-N is illustrated for the protein DinI, and torsion angles obtained by TALOS-N analysis from the measured chemical shifts of its backbone and 13Cβ nuclei are compared to those seen in a prior, experimentally determined structure. The program is also particularly useful for generating torsion angle restraints, which then can be used during standard NMR protein structure calculations. PMID:25502373

  14. Physical and chemical characterization of biochars derived from different agricultural residues

    NASA Astrophysics Data System (ADS)

    Jindo, K.; Mizumoto, H.; Sawada, Y.; Sanchez-Monedero, M. A.; Sonoki, T.

    2014-12-01

    Biochar is widely recognized as an efficient tool for carbon sequestration and soil fertility. The understanding of its chemical and physical properties, which are strongly related to the type of the initial material used and pyrolysis conditions, is crucial to identify the most suitable application of biochar in soil. A selection of organic wastes with different characteristics (e.g., rice husk (RH), rice straw (RS), wood chips of apple tree (Malus pumila) (AB), and oak tree (Quercus serrata) (OB)) were pyrolyzed at different temperatures (400, 500, 600, 700, and 800 °C) in order to optimize the physicochemical properties of biochar as a soil amendment. Low-temperature pyrolysis produced high biochar yields; in contrast, high-temperature pyrolysis led to biochars with a high C content, large surface area, and high adsorption characteristics. Biochar obtained at 600 °C leads to a high recalcitrant character, whereas that obtained at 400 °C retains volatile and easily labile compounds. The biochar obtained from rice materials (RH and RS) showed a high yield and unique chemical properties because of the incorporation of silica elements into its chemical structure. The biochar obtained from wood materials (AB and OB) showed high carbon content and a high absorption character.

  15. Efficiency of stepwise magnetic-chemical site assessment for fly ash derived heavy metal pollution

    NASA Astrophysics Data System (ADS)

    Cao, Liwan; Appel, Erwin; Rösler, Wolfgang; Magiera, Tadeusz

    2015-11-01

    Previous works revealed a close relationship between magnetic susceptibility (MS) and heavy metal (HM) contents originating from industrial sources. However, despite general statements on the usefulness of magnetic mapping, the benefit of this procedure for geochemistry was not quantified yet. We present a study on fly ash pollution in soil around a coal-burning power plant complex and simulate a stepwise approach of magnetic pre-screening and subsequent targeted sampling for chemical analysis. The aim of this study is not to discuss correlations between MS and HM, but to show that a combined stepwise magnetic-chemical approach is the most efficient way for outlining HM contamination. In order to provide quantitative evidence, we explored map similarities of spatial HM distributions based on magnetochemical data and chemical data only. We determined 3-D triangular planes defined by categorized HM values at the sampling coordinates and calculated the average dihedral angle of the normal vectors as a similarity result. The study shows that the `Targeted' HM map (selection of 30 sites based magnetic pre-screening) has a higher similarity with the `True' Pollution HM map (85 sites) than HM maps resulting from site selections (30 sites) without using magnetic pre-screening information.

  16. Use of terrestrial field studies in the derivation of bioaccumulation potential of chemicals.

    PubMed

    van den Brink, Nico W; Arblaster, Jennifer A; Bowman, Sarah R; Conder, Jason M; Elliott, John E; Johnson, Mark S; Muir, Derek C G; Natal-da-Luz, Tiago; Rattner, Barnett A; Sample, Bradley E; Shore, Richard F

    2016-01-01

    Field-based studies are an essential component of research addressing the behavior of organic chemicals, and a unique line of evidence that can be used to assess bioaccumulation potential in chemical registration programs and aid in development of associated laboratory and modeling efforts. To aid scientific and regulatory discourse on the application of terrestrial field data in this manner, this article provides practical recommendations regarding the generation and interpretation of terrestrial field data. Currently, biota-to-soil-accumulation factors (BSAFs), biomagnification factors (BMFs), and bioaccumulation factors (BAFs) are the most suitable bioaccumulation metrics that are applicable to bioaccumulation assessment evaluations and able to be generated from terrestrial field studies with relatively low uncertainty. Biomagnification factors calculated from field-collected samples of terrestrial carnivores and their prey appear to be particularly robust indicators of bioaccumulation potential. The use of stable isotope ratios for quantification of trophic relationships in terrestrial ecosystems needs to be further developed to resolve uncertainties associated with the calculation of terrestrial trophic magnification factors (TMFs). Sampling efforts for terrestrial field studies should strive for efficiency, and advice on optimization of study sample sizes, practical considerations for obtaining samples, selection of tissues for analysis, and data interpretation is provided. Although there is still much to be learned regarding terrestrial bioaccumulation, these recommendations provide some initial guidance to the present application of terrestrial field data as a line of evidence in the assessment of chemical bioaccumulation potential and a resource to inform laboratory and modeling efforts. PMID:26436822

  17. Parameter estimation in stochastic chemical kinetic models using derivative free optimization and bootstrapping

    PubMed Central

    Srivastava, Rishi; Rawlings, James B.

    2014-01-01

    Recent years have seen increasing popularity of stochastic chemical kinetic models due to their ability to explain and model several critical biological phenomena. Several developments in high resolution fluorescence microscopy have enabled researchers to obtain protein and mRNA data on the single cell level. The availability of these data along with the knowledge that the system is governed by a stochastic chemical kinetic model leads to the problem of parameter estimation. This paper develops a new method of parameter estimation for stochastic chemical kinetic models. There are three components of the new method. First, we propose a new expression for likelihood of the experimental data. Second, we use sample path optimization along with UOBYQA-Fit, a variant of of Powells unconstrained optimization by quadratic approximation, for optimization. Third, we use a variant of Efrons percentile bootstrapping method to estimate the confidence regions for the parameter estimates. We apply the parameter estimation method in an RNA dynamics model of E. coli. We test the parameter estimates obtained and the confidence regions in this model. The testing of the parameter estimation method demonstrates the efficiency, reliability, and accuracy of the new method. PMID:24920866

  18. Paleoclimatic significance of chemical weathering in loess-derived paleosols of subarctic central Alaska

    USGS Publications Warehouse

    Muhs, D.R.; Ager, T.A.; Skipp, G.; Beann, J.; Budahn, J.; McGeehin, J.P.

    2008-01-01

    Chemical weathering in soils has not been studied extensively in high-latitude regions. Loess sequences with modern soils and paleosols are present in much of subarctic Alaska, and allow an assessment of present and past chemical weathering. Five sections were studied in detail in the Fairbanks, Alaska, area. Paleosols likely date to mid-Pleistocene interglacials, the last interglacial, and early-to-mid-Wisconsin interstadiale. Ratios of mobile (Na, Ca, Mg, Si) to immobile (Ti or Zr) elements indicate that modern soils and most interstadial and interglacial paleosols are characterized by significant chemical weathering. Na2O/TiO2 is lower in modern soils and most paleosols compared to parent loess, indicating depletion of plagioclase. In the clay fraction, smectite is present in Tanana and Yukon River source sediments, but is absent or poorly expressed in modern soils and paleosols, indicating depletion of this mineral also. Loss of both plagioclase and smectite is well expressed in soils and paleosols as lower SiO 2/TiO2. Carbonates are present in the river source sediments, but based on CaO/TiO2, they are depleted in soils and most paleosols (with one exception in the early-to-mid-Wisconsin period). Thus, most soil-forming intervals during past interglacial and interstadial periods in Alaska had climatic regimes that were at least as favorable to mineral weathering as today, and suggest boreal forest or acidic tundra vegetation. ?? 2008 Regents of the University of Colorado.

  19. Protein structural information derived from NMR chemical shift with the neural network program TALOS-N.

    PubMed

    Shen, Yang; Bax, Ad

    2015-01-01

    Chemical shifts are obtained at the first stage of any protein structural study by NMR spectroscopy. Chemical shifts are known to be impacted by a wide range of structural factors, and the artificial neural network based TALOS-N program has been trained to extract backbone and side-chain torsion angles from (1)H, (15)N, and (13)C shifts. The program is quite robust and typically yields backbone torsion angles for more than 90 % of the residues and side-chain χ 1 rotamer information for about half of these, in addition to reliably predicting secondary structure. The use of TALOS-N is illustrated for the protein DinI, and torsion angles obtained by TALOS-N analysis from the measured chemical shifts of its backbone and (13)C(β) nuclei are compared to those seen in a prior, experimentally determined structure. The program is also particularly useful for generating torsion angle restraints, which then can be used during standard NMR protein structure calculations. PMID:25502373

  20. A quantitative analysis of weak intermolecular interactions & quantum chemical calculations (DFT) of novel chalcone derivatives

    NASA Astrophysics Data System (ADS)

    Chavda, Bhavin R.; Gandhi, Sahaj A.; Dubey, Rahul P.; Patel, Urmila H.; Barot, Vijay M.

    2016-05-01

    The novel chalcone derivatives have widespread applications in material science and medicinal industries. The density functional theory (DFT) is used to optimized the molecular structure of the three chalcone derivatives (M-I, II, III). The observed discrepancies between the theoretical and experimental (X-ray data) results attributed to different environments of the molecules, the experimental values are of the molecule in solid state there by subjected to the intermolecular forces, like non-bonded hydrogen bond interactions, where as isolated state in gas phase for theoretical studies. The lattice energy of all the molecules have been calculated using PIXELC module in Coulomb -London -Pauli (CLP) package and is partitioned into corresponding coulombic, polarization, dispersion and repulsion contributions. Lattice energy data confirm and strengthen the finding of the X-ray results that the weak but significant intermolecular interactions like C-H…O, Π- Π and C-H… Π plays an important role in the stabilization of crystal packing.

  1. Spectroscopic and quantum chemical studies on the structure of 2-arylquinoline-4(1 H)-thione derivatives

    NASA Astrophysics Data System (ADS)

    Mphahlele, Malose J.; El-Nahas, Ahmed M.; El-Gogary, Tarek M.

    2004-03-01

    The geometries of the title compounds were probed in solution, solid and gas states using spectroscopic methods, X-ray crystallography and quantum chemical techniques. The exclusive existence of the NH-4-thiones in solution (NMR and PCM-B3LYP(MP2)/6-31+G(d) calculations) and solid state (FT-IR and X-ray) is also corroborated by comparison of their spectroscopic data with those of the corresponding 2-aryl-1-methylquinoline-4(1 H)-thione derivatives. The co-existence of the quinoline-4-thione and quinoline-4-thiol (4-mercaptoquinoline) isomers in the gas phase is confirmed by mass spectrometry and the preponderance of the 4-thiol is supported by quantum chemical techniques (PM3, MP2 and B3LYP).

  2. A comparison of the chemical and liver extract-induced hepatic differentiation of adipose derived stem cells.

    PubMed

    Nhung, Truong Hai; Nam, Nguyen Hai; Nguyen, Nguyen Thi Kim; Nghia, Huynh; Van Thanh, Nguyen; Ngoc, Phan Kim; Van Pham, Phuc

    2015-11-01

    Adipose-derived stem cells (ADSCs) have been put forward as promising therapeutics for end-stage liver disease (ESLD). In the present study, we compared the effects of defined chemicals and liver extract on the hepatic differentiation of ADSCs. ADSCs were isolated according to the method described in our previously published study. Subsequently, the differentiation of ADSCs was induced separately by chemicals (including hepatic growth factor (HGF), fibroblast growth factor (FGF), and oncostatin M (OSM)) and liver extract (30 μg/ml) in a total period of 21 d. The efficiency of hepatic differentiation was evaluated by changes in the cell morphology, gene expression, and cellular function. The results showed that the liver extract promoted the hepatic differentiation of ADSCs to a significantly greater extent than the chemicals. In the group of ADSCs treated with liver extract, changes in the cell morphology began sooner, and the expression of alpha-FP and albumin genes was higher than that in the chemically treated group. The ADSCs in both the groups stained positive for anti-alpha trypsin (AAT) and albumin markers. The cells also exhibited glycogen storage capacity. Therefore, we concluded that the liver extract could efficiently induce the differentiation of ADSCs into hepatocyte-like cells. This study reveals the potential of mesenchymal stem cell differentiation in the liver extract, which supports further preclinical and clinical research on the application of ADSCs in ESLD treatment. PMID:26275888

  3. Characterization of Nitrogen-Containing Species in Coal and Petroleum-Derived Products by Ammonia Chemical Ionization-High Resolution Mass Spectrometry

    SciTech Connect

    Veloski, Garret A.; Lynn, Ronald J.; Sprecher, Richard F.

    1997-01-01

    A coal-derived light distillate and a petroleum-derived residuum have been studied by high resolution mass spectrometry using both low-pressure ammonia chemical ionization and low-voltage electron impact ionization. A mass calibration mixture for use with ammonia chemical ionization has been developed. Selective ionization of the basic nitrogen-containing compounds by ammonia chemical ionization and compound type characterization of the resulting quasi-molecular species has been demonstrated. Several homologous series of nitrogen-containing compounds were identified in a basic extract by electron impact ionization and compared with quasimolecular analogs identified by ammonia chemical ionization.

  4. The safety and efficacy of bacterial nanocellulose wound dressing incorporating sericin and polyhexamethylene biguanide: in vitro, in vivo and clinical studies.

    PubMed

    Napavichayanun, Supamas; Yamdech, Rungnapha; Aramwit, Pornanong

    2016-03-01

    In our previous work, we have attempted to develop a novel bacterial nanocellulose wound dressing which composed of both polyhexamethylene biguanide (PHMB) as an antimicrobial agent and sericin as an accelerative wound healing component. The loading sequence and concentration of PHMB and sericin were optimized to provide the wound dressing with the most effective antimicrobial activity and enhanced collagen production. In this study, further in vitro, in vivo, and clinical studies of this novel wound dressing were performed to evaluate its safety, efficacy, and applicability. For the in vitro cytotoxic test with L929 mouse fibroblast cells, our novel dressing was not toxic to the cells and also promoted cell migration as good as the commercially available dressing, possibly due to the component of sericin released. When implanted subcutaneously in rats, the lower inflammation response was observed for the novel dressing implanted, comparing to the commercially available dressing. This might be that the antimicrobial PHMB component of the novel dressing played a role to reduce infection and inflammation reaction. The clinical trial patch test was performed on the normal skin of healthy volunteers to evaluate the irritation effect of the dressing. Our novel dressing did not irritate the skin of any volunteers, as characterized by the normal levels of erythema and melanin and the absence of edema, papule, vesicle, and bullae. Then, the novel dressing was applied for the treatment of full-thickness wounds in rats. The wounds treated with our novel dressing showed significantly lower percentage of wound size and higher extent of collagen formation mainly due to the activity of sericin. We concluded that our novel bacterial nanocellulose incorporating PHMB and sericin was a safe and efficient wound dressing material for further investigation in the wound healing efficacy in clinic. PMID:26796543

  5. Physico-chemical studies of fused phenanthrimidazole derivative as sensitive NLO material

    NASA Astrophysics Data System (ADS)

    Jayabharathi, Jayaraman; Thanikachalam, Venugopal; Sathishkumar, Ramalingam; Jayamoorthy, Karunamoorthy

    2013-01-01

    Heterocyclic phenanthrimidazole derivative, 2-(4-fluorophenyl)-1-p-tolyl-1H-imidazo[4,5-f] [1,10] phenanthroline (FPTIP) has been synthesized and characterised by NMR, mass and CHN analysis. The FPTIP was evaluated concerning their solvatochromic properties and molecular optical nonlinearities. Their electric dipole moment (μ), polarizability (α) and hyperpolarizability (β) have been calculated theoretically and the results indicate that the extension of the π-framework of the ligands has an effect on the NLO properties. The energies of the HOMO and LUMO levels and the molecular electrostatic potential (MEP) energy surface studies have exploited the existence of intramolecular charge transfer (ICT) within the molecule.

  6. Chemically authentic surrogate mixture model for the thermophysical properties of a coal-derived liquid fuel

    SciTech Connect

    M.L. Huber; E.W. Lemmon; V. Diky; B.L. Smith; T.J. Bruno

    2008-09-15

    We developed a surrogate mixture model to represent the physical properties of a coal-derived liquid fuel using only information obtained from a gas chromatography-mass spectrometry analysis of the fuel and a recently developed 'advanced distillation curve'. We then predicted the density, speed of sound, and viscosity of the fuel and compared them to limited experimental data. The surrogate contains five components (n-propylcyclohexane, trans-decalin, {alpha}-methyldecalin, bicyclohexane, and n-hexadecane), yet comparisons to limited experimental data demonstrate that the model is able to represent the density, sound speed, and viscosity to within 1, 4, and 5%, respectively. 102 refs., 2 figs., 5 tabs.

  7. Chemical modeling of acid-base properties of soluble biopolymers derived from municipal waste treatment materials.

    PubMed

    Tabasso, Silvia; Berto, Silvia; Rosato, Roberta; Marinos, Janeth Alicia Tafur; Ginepro, Marco; Zelano, Vincenzo; Daniele, Pier Giuseppe; Montoneri, Enzo

    2015-01-01

    This work reports a study of the proton-binding capacity of biopolymers obtained from different materials supplied by a municipal biowaste treatment plant located in Northern Italy. One material was the anaerobic fermentation digestate of the urban wastes organic humid fraction. The others were the compost of home and public gardening residues and the compost of the mix of the above residues, digestate and sewage sludge. These materials were hydrolyzed under alkaline conditions to yield the biopolymers by saponification. The biopolymers were characterized by 13C NMR spectroscopy, elemental analysis and potentiometric titration. The titration data were elaborated to attain chemical models for interpretation of the proton-binding capacity of the biopolymers obtaining the acidic sites concentrations and their protonation constants. The results obtained with the models and by NMR spectroscopy were elaborated together in order to better characterize the nature of the macromolecules. The chemical nature of the biopolymers was found dependent upon the nature of the sourcing materials. PMID:25658795

  8. Chemical Modeling of Acid-Base Properties of Soluble Biopolymers Derived from Municipal Waste Treatment Materials

    PubMed Central

    Tabasso, Silvia; Berto, Silvia; Rosato, Roberta; Tafur Marinos, Janeth Alicia; Ginepro, Marco; Zelano, Vincenzo; Daniele, Pier Giuseppe; Montoneri, Enzo

    2015-01-01

    This work reports a study of the proton-binding capacity of biopolymers obtained from different materials supplied by a municipal biowaste treatment plant located in Northern Italy. One material was the anaerobic fermentation digestate of the urban wastes organic humid fraction. The others were the compost of home and public gardening residues and the compost of the mix of the above residues, digestate and sewage sludge. These materials were hydrolyzed under alkaline conditions to yield the biopolymers by saponification. The biopolymers were characterized by 13C NMR spectroscopy, elemental analysis and potentiometric titration. The titration data were elaborated to attain chemical models for interpretation of the proton-binding capacity of the biopolymers obtaining the acidic sites concentrations and their protonation constants. The results obtained with the models and by NMR spectroscopy were elaborated together in order to better characterize the nature of the macromolecules. The chemical nature of the biopolymers was found dependent upon the nature of the sourcing materials. PMID:25658795

  9. Fabrication of large-area arrays of hybrid nanostructures on polymer-derived chemically patterned surfaces

    NASA Astrophysics Data System (ADS)

    Liu, Xiaoying; Nepal, Dhriti; Biswas, Sushmita; Park, Kyoungweon; Vaia, Richard; Nealey, Paul; Air Force Research Laboratories Collaboration; University of Chicago Team

    2014-03-01

    The precise placement and assembly of nanoparticles (NPs) into large-area nanostructure arrays will allow for the design and implementation of advanced nanoscale devices for applications in fields such as quantum computing, optical sensing, superlenses, photocatalysis, photovoltaics, and non-linear optics. Our work is focused on using chemically nanopatterned surfaces to fabricate arrays of hybrid nanostructures with each component of the building block at well-defined positions. The precise chemical contrast patterns with densities and resolution of features created using standard tools of lithography, polymer self-assembly, and surface functionalization allow for control of position and interparticle spacing through selective surface-particle and particle-particle interactions. We have demonstrated the assembly of NPs, including metallic NPs and semiconductor quantum dots, into arrays of hybrid structures with various geometries, such as monomers, dimers, quatrefoils, stripes, and chains. We have developed protocols to fabricate NP arrays over a variety of substrates, which allows for the design and characterization of optical and electronic nanostructures and devices to meet the requirements of various technological applications.

  10. Chemical constituents of marine algal-derived endophytic fungus Exophiala oligosperma EN-21

    NASA Astrophysics Data System (ADS)

    Li, Fang; Li, Ke; Li, Xiaoming; Wang, Bingui

    2011-01-01

    Seven compounds (1-7) were identified from the cultivation of the endophytic fungus Exophiala oligosperma (EN-21) that was isolated from the inner tissue of the marine red alga Laurencia similis. Their structures were identified with spectroscopic and chemical methods as 2-phenoxynaphthalene ( 1), (2 S, 3 R, 4 E, 8 E)-1- O-β-D-glucopyranosyl-3-hydroxy-2-[( R)-2'-hydroxyoctadecanoyl] amino-9-methyl-4, 8-octadeca-diene ( 2), (22 E,24 R)-ergosta-7,22-dien-3β,5α,6β-triol ( 3), (22 E, 24 R)-3β, 5α, 9α-trihydroxy-ergosta-7, 22-dien-6-one ( 4), (22 E, 24 R)-5α, 6α-epoxy-ergosta-8, 22-dien-3β, 7α-diol ( 5), (22 E, 24 R)-ergosta-4, 6, 8(14), 22-tetraen-3-one ( 6), and euphorbol ( 7). This paper reports for the first time the chemical constituents of fungus Exophiala oligosperma and the discovery of compound 1 as a natural product from the fungus.

  11. Biocomposites from waste derived biochars: Mechanical, thermal, chemical, and morphological properties.

    PubMed

    Das, Oisik; Sarmah, Ajit K; Bhattacharyya, Debes

    2016-03-01

    To identify a route for organic wastes utilisation, biochar made from various feedstocks (landfill pine saw dust, sewage sludge, and poultry litter) and at diverse pyrolysis conditions, were collected. These biochars were used to fabricate wood and polypropylene biocomposites with a loading level of 24 mass%. The composites were tested for their mechanical, chemical, thermal, morphological, and fire properties. The poultry litter biochar biocomposite, with highest ash content, was found to have high values of tensile/flexural strength, tensile/flexural modulus, and impact strength, compared to other composites. In general, addition of all the biochars enhanced the tensile/flexural moduli of the composites. The crystal structure of polypropylene in the composite was intact after the incorporation of all the biochars. The final chemical and crystal structure of the composite were an additive function of the individual components. The biochar particles along with wood acted as nucleating agents for the recrystallization of polypropylene in composite. Each component in the composites was found to decompose individually under thermal regime. The electron microscopy revealed the infiltration of polypropylene into the biochar pores and a general good dispersion in most composites. The poultry litter composite was found to have lower heat release rate under combustion regime. PMID:26724232

  12. Chemical synthesis, in vitro acetohydroxyacid synthase (AHAS) inhibition, herbicidal activity, and computational studies of isatin derivatives.

    PubMed

    Wang, Jianguo; Tan, Haizhong; Li, Yonghong; Ma, Yi; Li, Zhengming; Guddat, Luke W

    2011-09-28

    Acetohydroxyacid synthase (AHAS) catalyzes the first common step in the biosynthesis of the branched-chain amino acids. As a result of its metabolic importance in plants, it is a target for many commercial herbicides. Virtual screening analysis inspired the evaluation of 19 commercially available isatin analogues and 13 newly synthesized isatin derivatives as novel AHAS inhibitors and for their herbicidal activity. The best compound demonstrated 95% inhibition of the activity of Arabidopsis thaliana AHAS at a concentration of 100 mg L(-1), whereas the herbicidal activities of three compounds reached 50% inhibition at a concentration of 10 mg L(-1) using the rape root growth test. CoMFA contour models were established to understand the structure-activity relationships for this class of AHAS inhibitor. The compounds were docked to the active site cavity of A. thaliana AHAS using FlexX, and the dominant binding mode was consistent with frontier molecular orbital from DFT calculations. This is the first comprehensive study of isatin derivatives as AHAS inhibitors and provides a valuable starting point for the design of new herbicides. PMID:21838297

  13. Identification of persisten anionic surfactant-derived chemicals in sewage effluent and groundwater

    USGS Publications Warehouse

    Field, J.A.; Leenheer, J.A.; Thorn, K.A.; Barber, L.B., II; Rostad, C.; Macalady, D.L.; Daniel, S.R.

    1992-01-01

    Preparative isolation and fractionation procedures coupled with spectrometric analyses were used to identify surfactant-derived contaminants in sewage effluent and sewage-contaminated groundwater from a site located on Cape Cod, Massachusetts. Anionic surfactants and their biodegradation intermediates were isolated from field samples by ion exchange and fractionated by solvent extraction and adsorption chromatography. Fractions were analyzed by 13C nuclear magnetic resonance spectrometry and gas chromatography-mass spectrometry. Carboxylated residues of alkylphenol polyethoxylate surfactants were detected in sewage effluent and contaminated groundwater. Linear alkylbenzenesulfonates (LAS) were identified in sewage effluent and groundwater. Groundwater LAS composition suggested preferential removal of select isomers and homologs due to processes of biodegradation and partitioning. Tetralin and indane sulfonates (DATS), alicyclic analogs of LAS, were also identified in field samples. Although DATS are a minor portion of LAS formulations, equivalent concentrations of LAS and DATS in groundwater suggested persistence of alicyclic contaminant structures over those of linear structure. Sulfophenyl-carboxylated (SPC) LAS biodegradation intermediates were determined in sewage effluent and groundwater. Homolog distributions suggested that SPC containing 3-10 alkyl-chain carbons persist during infiltration and groundwater transport. Surfactant-derived residues detected in well F300-50 groundwater have a minimum residence time in the range of 2.7-4.6 yr. LAS detected in groundwater at 500 m from infiltration has been stable over an estimated 50-500 half lives.

  14. Comparison of emission rate values for odour and odorous chemicals derived from two sampling devices

    NASA Astrophysics Data System (ADS)

    Hudson, N.; Ayoko, G. A.

    Field and laboratory measurements identified a complex relationship between odour emission rates provided by the US EPA dynamic emission chamber and the University of New South Wales wind tunnel. Using a range of model compounds in an aqueous odour source, we demonstrate that emission rates derived from the wind tunnel and flux chamber are a function of the solubility of the materials being emitted, the concentrations of the materials within the liquid; and the aerodynamic conditions within the device - either velocity in the wind tunnel, or flushing rate for the flux chamber. The ratio of wind tunnel to flux chamber odour emission rates (OU m -2 s) ranged from about 60:1 to 112:1. The emission rates of the model odorants varied from about 40:1 to over 600:1. These results may provide, for the first time, a basis for the development of a model allowing an odour emission rate derived from either device to be used for odour dispersion modelling.

  15. Activation of the germ-cell potential of human bone marrow-derived cells by a chemical carcinogen

    PubMed Central

    Liu, Chunfang; Ma, Zhan; Xu, Songtao; Hou, Jun; Hu, Yao; Yu, Yinglu; Liu, Ruilai; Chen, Zhihong; Lu, Yuan

    2014-01-01

    Embryonic/germ cell traits are common in malignant tumors and are thought to be involved in malignant tumor behaviors. The reasons why tumors show strong embryonic/germline traits (displaced germ cells or gametogenic programming reactivation) are controversial. Here, we show that a chemical carcinogen, 3-methyl-cholanthrene (3-MCA), can trigger the germ-cell potential of human bone marrow-derived cells (hBMDCs). 3-MCA promoted the generation of germ cell-like cells from induced hBMDCs that had undergone malignant transformation, whereas similar results were not observed in the parallel hBMDC culture at the same time point. The malignant transformed hBMDCs spontaneously and more efficiently generated into germ cell-like cells even at the single-cell level. The germ cell-like cells from induced hBMDCs were similar to natural germ cells in many aspects, including morphology, gene expression, proliferation, migration, further development, and teratocarcinoma formation. Therefore, our results demonstrate that a chemical carcinogen can reactivate the germline phenotypes of human somatic tissue-derived cells, which might provide a novel idea to tumor biology and therapy. PMID:24998261

  16. Assimilation of satellite-derived NO2 data into a chemical transport model

    NASA Astrophysics Data System (ADS)

    Silver, Jeremy; Brandt, Jrgen; Hvidberg, Martin; Frydendall, Jan

    2010-05-01

    The Danish Eulerian Hemispheric Model (DEHM) is a three-dimensional chemical transport model that can simulate emission, transport, diffusion, chemistry and deposition processes of air pollutant species in the atmosphere. A data assimilation (DA) module was added to DEHM, to assimilate estimates of tropospheric NO2 concentrations. The observations were obtained from the Ozone Monitoring Instrument (OMI) aboard the NASA satellite Aura. The assimilation schemed was based on statistical interpolation. We conducted several experiments, modifying the parameterisation of the background and observation error covariance matrices. Results from these experiments were compared with an independent data set: ground-based measurements of NO2 and O3 from the European Monitoring and Evaluation Programme. Despite the simplicity of the DA scheme, it substantially improved the accuracy of predicted ground-level concentrations compared to those calculated without DA. Furthermore, after applying the DA module, temporal variation in NO2 concentrations was more accurately modelled by DEHM.

  17. Chemical Characteristics, Synthetic Methods, and Biological Potential of Quinazoline and Quinazolinone Derivatives

    PubMed Central

    2014-01-01

    The heterocyclic fused rings quinazoline and quinazolinone have drawn a huge consideration owing to their expanded applications in the field of pharmaceutical chemistry. Quinazoline and quinazolinone are reported for their diversified biological activities and compounds with different substitutions bring together to knowledge of a target with understanding of the molecule types that might interact with the target receptors. Quinazolines and quinazolinones are considered as an important chemical for the synthesis of various physiological significance and pharmacological utilized molecules. Quinazolines and quinazolinone are a large class of biologically active compounds that exhibited broad spectrum of biological activities such as anti-HIV, anticancer, antifungal, antibacterial, antimutagenic, anticoccidial, anticonvulsant, anti-inflammatory, antidepressant, antimalarial, antioxidant, antileukemic, and antileishmanial activities and other activities. Being considered as advantaged scaffold, the alteration is made with different substituent. PMID:25692041

  18. Direct Chemical Vapor Deposition-Derived Graphene Glasses Targeting Wide Ranged Applications.

    PubMed

    Sun, Jingyu; Chen, Yubin; Priydarshi, Manish Kr; Chen, Zhang; Bachmatiuk, Alicja; Zou, Zhiyu; Chen, Zhaolong; Song, Xiuju; Gao, Yanfeng; Rümmeli, Mark H; Zhang, Yanfeng; Liu, Zhongfan

    2015-09-01

    Direct growth of graphene on traditional glasses is of great importance for various daily life applications. We report herein the catalyst-free atmospheric-pressure chemical vapor deposition approach to directly synthesizing large-area, uniform graphene films on solid glasses. The optical transparency and sheet resistance of such kinds of graphene glasses can be readily adjusted together with the experimentally tunable layer thickness of graphene. More significantly, these graphene glasses find a broad range of real applications by enabling the low-cost construction of heating devices, transparent electrodes, photocatalytic plates, and smart windows. With a practical scalability, the present work will stimulate various applications of transparent, electrically and thermally conductive graphene glasses in real-life scenarios. PMID:26305883

  19. Fluid flow in the Rotorua geothermal field derived from isotopic and chemical data

    SciTech Connect

    Stewart, M.K.; Lyon, G.L.; Robinson, B.W. ); Glover, R.B. )

    1992-04-01

    A wide variety of isotopic and chemical measurements on geothermal fluids from shallow wells at Rotorua have given the following interpretations: The Rotorua field comprises one geothermal system; a primary upflow of (outgassed) alkali chloride water extends from northeast Whakarewarewa to Ngapuna and under Lake Rotorua (east side of the system). At the southern end a secondary upflow discharges dilute alkali chloride water; a second major upflow at Kuirau-Ohinmutu discharges chloride-bicarbonate waters formed by dilution of the primary water and reaction with rock; boiling primary water flows from the eastern upflow zone under confining sediments into aquifers in Rotorua Rhyolite containing chloride-bicarbonate waters in the central region; tritium-bearing groundwater penetrates from overlying aquifers in the sediment into the saddle area between the rhyolite domes or along the crest of the southern rhyolite dome and flows northeast into the northern dome.

  20. Oxygen carrier development for chemical looping combustion of coal derived synthesis gas

    SciTech Connect

    Siriwardane, R.V.; Chaudhari, K.; Zinn, A.N.; Simonyi, T.; Robinson, Clark; Poston, J.A.

    2006-09-01

    In the present work, NETL researchers have studied chemical looping combustion (CLC) with an oxygen carrier NiO/bentonite (60 wt.% NiO) for the IGCC systems utilizing simulated synthesis gas. Multi cycle CLC was conducted with NiO/Bentonite in TGA at atmospheric pressure and in a high pressure reactor in a temperature range between 700-900°C. Global reaction rates of reduction and oxidation as a function of conversion were calculated for all oxidation-reduction cycles utilizing the TGA data. The effect of particle size of the oxygen carrier on CLC was studied for the size between 20-200 mesh. The multi cycle CLC tests conducted in a high pressure packed bed flow reactor indicated constant total production of CO2 from fuel gas at 800°C and 900°C and full consumption of hydrogen during the reaction.

  1. Physical and chemical characterizations of biochars derived from different agricultural residues

    NASA Astrophysics Data System (ADS)

    Jindo, K.; Mizumoto, H.; Sawada, Y.; Sanchez-Monedero, M. A.; Sonoki, T.

    2014-08-01

    Biochar has received large attention as a strategy to tackle against carbon emission. Not only carbon fixation has been carried out but also other merits for agricultural application due to unique physical and chemical character such as absorption of contaminated compounds in soil, trapping ammonia and methane emission from compost, and enhancement of fertilizer quality. In our study, different local waste feed stocks (rice husk, rice straw, wood chips of apple tree (Malus Pumila) and oak tree (Quercus serrata)), in Aomori, Japan, were utilized for creating biochar with different temperature (400-800 °C). Concerning to the biochar production, the pyrolysis of lower temperature had more biochar yield than higher temperature pyrolysis process. On the contrary, surface areas and adsorption characters have been increased as increasing temperature. The proportions of carbon content in the biochars also increased together with increased temperatures. Infrared-Fourier spectra (FT-IR) and 13C-NMR were used to understand carbon chemical compositions in our biochars, and it was observed that the numbers of the shoulders representing aromatic groups, considered as stable carbon structure appeared as the temperature came closer to 600 °C, as well as in FT-IR. In rice materials, the peak assigned to SiO2, was observed in all biochars (400-800 °C) in FT-IR. We suppose that the pyrolysis at 600 °C creates the most recalcitrant character for carbon sequestration, meanwhile the pyrolysis at 400 °C produces the superior properties as a fertilizer by retaining volatile and easily labile compounds which promotes soil microbial activities.

  2. Isolation and partial chemical characterization of macrophage-derived neutrophil chemotactic factor

    PubMed Central

    Dias-Baruffi, M.; Cunha, F. Q.; Ferreira, S. H.

    1995-01-01

    Macrophages stimulated with lipopolysaccharide (LPS) release a factor (MNCF; macrophage-derived neutrophil chemotactic factor) which induces neutrophil migration in vivo and in vitro. The in vivo chemotactic activity of crude MNCF is not affected by pretreating the animals with dexamethasone, an uncommon characteristic which discriminates MNCF from known chemotactic cytokines. We purified MNCF by affinity chromatography of the supernatant from LPS-stimulated macrophages on immobilized D-galactose, followed by gel filtration of the sugar-binding material on Superdex 75. The activity was eluted in the volume corresponding to a MW of 54 kDa. SDS–PAGE of this preparation revealed a single band, also corresponding to a 54 kDa protein. MNCF is an acidic protein (pI < 4) as shown by chromatofocussing. Like the crude MNCF, the homogeneous protein induced neutrophil migration in vitro as well as in vivo. This was not modified by dexamethasone pretreatment. PMID:18475648

  3. The optical properties and quantum chemical calculations of thienyl and furyl derivatives of pyrene.

    PubMed

    Idzik, Krzysztof R; Cywiński, Piotr J; Kuznik, Wojciech; Frydel, Jaroslaw; Licha, Tobias; Ratajczyk, Tomasz

    2015-09-21

    A detailed electrochemical, photophysical and theoretical study is presented for various new thienyl and furyl derivatives of pyrene. Their optical properties are described based on UV-VIS absorption and both steady-state and time-resolved fluorescence spectroscopy. DFT and TDDFT calculations are also presented to support experimental data. The calculations results show that HOMO-LUMO orbitals are delocalized uniformly between aromatic core and aryl substituents. Good electrochemical stability of thienyl and furyl hybrids of pyrene confirm their potential application for light emitting electrochemical cells or spintronics mainly due to their beneficial optical and charge transport properties in electrochromic devices. In order to demonstrate this potential, an OLED device is presented. Synthesized compounds included in this OLED device both facilitate electron transport and act as a light emitting layer. PMID:26257127

  4. Surface Chemical Gradient Affects the Differentiation of Human Adipose-Derived Stem Cells via ERK1/2 Signaling Pathway.

    PubMed

    Liu, Xujie; Shi, Shengjun; Feng, Qingling; Bachhuka, Akash; He, Wei; Huang, Qianli; Zhang, Ranran; Yang, Xing; Vasilev, Krasimir

    2015-08-26

    To understand the role of surface chemistry on cell behavior and the associated molecular mechanisms, we developed and utilized a surface chemical gradient of amine functional groups by carefully adjusting the gas composition of 1,7-octadiene (OD) and allylamine (AA) of the plasma phase above a moving substrate. The chemical gradient surface used in the present work shows an increasing N/C ratio and wettability from the OD side toward the AA side with no change in surface topography. Under standard culture conditions (with serum), human adipose-derived stem cells (hASCs) adhesion and spreading area increased toward the AA side of the gradient. However, there were no differences in cell behavior in the absence of serum. These results, supported by the trends in proteins adsorption on the gradient surface, demonstrated that surface chemistry affects the response of hASCs through cell-adhesive serum proteins, rather than interacting directly with the cells. The expression of p-ERK and the osteogenic differentiation increased toward the AA side of the gradient, while adipogenic differentiation decreased in the same direction; however, when the activation of ERK1/2 was blocked by PD98059, the levels of osteogenic or adipogenic differentiation on different regions of the chemical gradient were the same. This indicates that ERK1/2 may be an important downstream signaling pathway of surface chemistry directed stem cell fate. PMID:26237746

  5. The Microstructure, Chemical Characteristic and Crystallization Behavior of the Polymer Derived Si-B-C-N Amorphous Ceramic

    NASA Astrophysics Data System (ADS)

    Gao, Dond; Zhang, Fanwei; Zhang, Yue; Song, Yang; Shi, Xiaobin

    Amorphous materials of the Si-(B)-C-N system have recently attracted considerable interest because of its hardness, low density, durability at extremely high temperature and easy to be prepared from precursor compounds by polymer route. The materials show a great potential to be used in the field of the Thermal Protective System (TPS) for the aircrafts, while the microstructure and chemical configuration are still not clearly revealed due to its complicated covalent character for this multi-component amorphous material. This paper focused on the characterization of polymer derived Si-(B)-C-N amorphous ceramic, various method were employed in order to obtain accurate information about the microstructure, chemical composition, bonding mode of components, such as TEM, EPMA, NMR and FT-IR. SiC crystalline was found existing in the amorphous glass, which indicates the preparation process was achieved accompanied by crystallization of SiC from polymer precursor. The microstructure of the researched material was analyzed and relative accurate chemical composition was obtained on the basis of characterization result, furthermore the covalent character of the amorphous material was deduced according to the characterization results obtained.

  6. Multiple microRNAs derived from chemically synthesized precursors regulate thrombospondin 1 expression.

    PubMed

    Dogar, Afzal M; Semplicio, Giuseppe; Guennewig, Boris; Hall, Jonathan

    2014-04-01

    Thrombospondin 1 (THBS1) is a secreted protein with a variety of biological functions, including a potent anti-angiogenic activity and activation of latent transforming growth factor beta (TGF-β). In many human cancers it is expressed at low levels, although mutations in the THBS1 gene have been rarely reported. Instead, the loss of THBS1 expression has been proposed to be due to transcriptional and post-transcriptional deregulations. In a systematic screen of predicted microRNA (miRNA) binding sites in the THBS1 3' untranslated region (UTR) we employed chemically synthesized pre-miRNAs-a new class of pre-miRNA mimics-to show that several miRNAs (let-7a, miR-18a, miR-29b, miR-194, and miR-221) can modulate THBS1 expression at the post-transcriptional level. Sequence-specific downregulation of THBS1 by let-7a, miR-18a or by a small interfering RNA induced TGF-β1 and SMAD4 transcript levels. Ectopic expression of latent TGF-β1 reduced THBS1 protein expression and was associated with increased expression of let-7a, let-7-b, and miR-18a in cells. These data suggest an inverse correlation of THBS1 and latent TGF-β1 expression levels possibly involving miRNAs. PMID:24444023

  7. Production of levulinic acid and use as a platform chemical for derived products

    SciTech Connect

    Bozell, J.J.; Moens, L.; Elliott, D.C.; Wang, Y.; Neuenscwander, G.G.; Fitzpatrick, S.W.; Bilski, R.J.; Jarnefeld, J.L.

    1999-07-01

    Levulinic acid (LA) can be produced cost effectively and in high yield from renewable feedstocks in a new industrial process. The technology is being demonstrated on a one ton/day scale at a facility in South Glens Falls, New York. Low cost LA can be used as a platform chemical for the production of a wide range of value-added products. This research has demonstrated that LA can be converted to methyltetrahydrofuran (MTHF), a solvent and fuel extender. MTHF is produced in {gt}80% molar yield via a single stage catalytic hydrogenation process. A new preparation of {delta}-aminolevulinic acid (DALA), a broad spectrum herbicide from LA has also been developed. Each step in this new process proceeds in high ({gt}80%) yield and affords DALA (as the hydrochloride salt) in greater than 90% purity, giving a process that could be commercially viable. LA is also being investigated as a starting material for the production of diphenolic acid (DPA), a direct replacement for bisphenol A.

  8. Chemical Abundances of NGC 5461 and NGC 5471 Derived from Echelle Spectrophotometry

    NASA Astrophysics Data System (ADS)

    Luridiana, V.; Esteban, C.; Peimbert, M.; Peimbert, A.

    2002-04-01

    We present high resolution spectroscopic data of the two giant extragalactic H II regions NGC 5461 and NGC 5471 in M101, which have been obtained with the 2.1-m telescope of the Observatorio Astronómico Nacional in San Pedro Martir, Baja California. We measured the intensities of several H and He recombination lines, and of forbidden lines of a large number of ions. We calculate the physical conditions in the two nebulae with a large number of diagnostics and determine their chemical abundances by applying ionization correction factors ( icf's) to the observed ionic abundances. For NGC 5461, the icf's are based on a tailored photoionization model of the region (Luridiana & Peimbert 2001), while for NGC 5471 they are computed from those predicted by a photoionization model of NGC 2363 (Luridiana, Peimbert, & Leitherer 1999), a region which is similar to NGC 5471 in the ionization structure. For both regions, the icf's are compared to those computed following the prescriptions by Mathis & Rosa (1991). Such comparison shows large discrepancies for several elements, including nitrogen, neon, and chlorine.

  9. Characterisation of waste derived biochar added biocomposites: chemical and thermal modifications.

    PubMed

    Das, Oisik; Sarmah, Ajit K; Zujovic, Zoran; Bhattacharyya, Debes

    2016-04-15

    A step towards sustainability was taken by incorporating waste based pyrolysed biochar in wood and polypropylene biocomposites. The effect of biochar particles on the chemistry and thermal makeup of the composites was determined by characterising them through an array of characterisation techniques such as 3D optical profiling, X-ray diffraction, transmission electron microscopy, electron spin/nuclear magnetic resonance spectroscopy, and differential scanning calorimetry. It was observed that addition of biochar increased the presence of free radicals in the composite while also improving its thermal conductivity. Biochar particles did not interfere with the melting behaviour of polymer in the thermal regime. However, wood and biochar acted as nucleation agents consequently increasing the crystallisation temperature. The crystal structure of polypropylene was not disrupted by biochar inclusion in composite. Transmission electron microscopy images illustrated the aggregated nature of the biochar particles at higher loading levels. Nuclear magnetic resonance studies revealed the aromatic nature of biochar and the broadening of peak intensities of composites with increasing biochar levels due to its amorphous nature and presence of free radicals. Thus, this insight into the chemical and thermal modification of biochar added composites would allow effective engineering to optimise their properties while simultaneously utilising wastes. PMID:26808404

  10. Process related effects on the chemical and toxicologic characteristics of coal derived fuels

    SciTech Connect

    Wright, C.W.; Chess, E.K.; Bean, R.M.; Mahlum, D.D.; Stewart, D.L.; Wilson, B.W.

    1986-01-01

    As a component of an ongoing program to assess the potential health effects of coal conversion materials, we have recently completed chemical and toxicologic studies of a sample set collected on selected days of a 25-day demonstration run of a catalytic two stage direct coal liquefaction (CTSL) process. There was an increase in heteroatomic, nitrogen containing polycyclic aromatic compounds (NPAC) and hydroxy-substituted PAC, compounds as the operation time of the pilot plant increased. The proportion of material which boiled above 975/sup 0/F also increased in the solids-free portion of the recycle slurry oil as pilot plant operation time increased. As anticipated from the increase in NPAC concentration during the run, the microbial mutagenic activity of selected process materials also increased as a function of run time. Likewise, the tumorigenicity of the materials produced later in the demonstration run was higher than that of those produced initially. These results support the view that catalyst deactivation during the course of the run gives rise not only to lower coal conversion, but also to increased toxicologic activity. 9 refs., 3 figs., 3 tabs.

  11. Quantum chemical and statistical study of megazol-derived compounds with trypanocidal activity

    NASA Astrophysics Data System (ADS)

    Rosselli, F. P.; Albuquerque, C. N.; da Silva, A. B. F.

    In this work we performed a structure-activity relationship (SAR) study with the aim to correlate molecular properties of the megazol compound and 10 of its analogs with the biological activity against Trypanosoma cruzi (trypanocidal or antichagasic activity) presented by these molecules. The biological activity indication was obtained from in vitro tests and the molecular properties (variables or descriptors) were obtained from the optimized chemical structures by using the PM3 semiempirical method. It was calculated ˜80 molecular properties selected among steric, constitutional, electronic, and lipophilicity properties. In order to reduce dimensionality and investigate which subset of variables (descriptors) would be more effective in classifying the compounds studied, according to their degree of trypanocidal activity, we employed statistical methodologies (pattern recognition and classification techniques) such as principal component analysis (PCA), hierarchical cluster analysis (HCA), K-nearest neighbor (KNN), and discriminant function analysis (DFA). These methods showed that the descriptors molecular mass (MM), energy of the second lowest unoccupied molecular orbital (LUMO+1), charge on the first nitrogen at substituent 2 (qN'), dihedral angles (D1 and D2), bond length between atom C4 and its substituent (L4), Moriguchi octanol-partition coefficient (MLogP), and length-to-breadth ratio (L/Bw) were the variables responsible for the separation between active and inactive compounds against T. cruzi. Afterwards, the PCA, KNN, and DFA models built in this work were used to perform trypanocidal activity predictions for eight new megazol analog compounds.

  12. The potential of synthetic indolylquinoline derivatives for Aβ aggregation reduction by chemical chaperone activity.

    PubMed

    Chang, Kuo-Hsuan; Chiu, Ya-Jen; Chen, Shu-Ling; Huang, Chen-Hsiang; Lin, Chih-Hsin; Lin, Te-Hsien; Lee, Chi-Mei; Ramesh, Chintakunta; Wu, Chung-Hsin; Huang, Chin-Chang; Fung, Hon-Chung; Chen, Yi-Chun; Lin, Jung-Yaw; Yao, Ching-Fa; Huang, Hei-Jen; Lee-Chen, Guey-Jen; Lee, Ming-Chung; Hsieh-Li, Hsiu Mei

    2016-02-01

    Alzheimer's disease (AD) is the most prevalent form of dementia associated with progressive cognitive decline and memory loss. Extracellular β-amyloid (Aβ) is a major constituent of senile plaques, one of the pathological hallmarks of AD. Aβ deposition causes neuronal death via a number of possible mechanisms such as increasing oxidative stress. Therefore therapeutic approaches to identify novel Aβ aggregate reducers could be effective for AD treatment. Using a Trx-His-Aβ biochemical assay, we screened 11 synthetic indolylquinoline compounds, and found NC009-1, -2, -6 and -7 displaying potential to reduce Aβ aggregation. Treating Tet-On Aβ-GFP 293 cells with these compounds reduced Aβ aggregation and reactive oxygen species. These compounds also promoted neurite outgrowth in Tet-On Aβ-GFP SH-SY5Y cells. Furthermore, treatment with above compounds improved neuronal cell viability, neurite outgrowth, and synaptophysin expression level in mouse hippocampal primary culture under oligomeric Aβ-induced cytotoxicity. Moreover, the tested NC009-1 significantly ameliorated Aβ-induced inhibition of hippocampal long-term potentiation in mouse hippocampal slices. Our results demonstrate how synthetic indolylquinoline compounds are likely to work as chemical chaperones in Aβ-aggregation reduction and neuroprotection, providing insight into the possible applications of indolylquinoline compounds in AD treatment. PMID:26362358

  13. Chemically derived defects in zinc oxide nanocrystals and their enhanced photo-electrocatalytic activities.

    PubMed

    Prakash, Anand; Bahadur, D

    2014-10-21

    This paper reports the influence of surface defects on the photocatalytic degradation of methylene blue (MB) for zinc oxide (ZnO) nanocrystals (NCs) synthesized in different organic solvents. A simple chemical approach has been adopted for the promotion of oxygen vacancies in pristine ZnO using solvents namely dimethylformamide (DMF), N-methyl-2-pyrrolidone (NMP) and dimethylsulfoxide (DMSO). This alters the growth of NCs through the promotion of oxygen vacancies depending on the fact that the solvent with minimum viscosity supports faster nucleation and growth exhibiting maximum surface defects. DMF with minimum viscosity results in largest particle size and superior photocatalytic activity. Further, X-ray diffraction, UV-visible reflectance spectroscopy and transmission electron microscopy confirm that the DMF supports the faster growth of NCs as compared to NMP and DMSO. Electron paramagnetic resonance, Raman, X-ray photoelectron, and photoluminescence spectroscopies confirm different states of oxygen vacancies in the NCs and their dependence on the nature of solvents. The photocatalytic activities of these NCs were investigated against the degradation of MB as a model dye. The results show that the oxygen defects at the surface of NCs are more responsible for higher photocatalytic activity than the specific surface area of NCs. The electrochemical investigations of MB degradation suggest that these defects upon interaction with MB influence the storage capacity and charge-discharge profiles of NCs. During degradation, MB passivates these defects, which has been explained in terms of increased charge-discharge time and storage capacity. PMID:25183397

  14. Chemical structure and pharmacological activity of some derivatives of digitoxigenin and digoxigenin

    PubMed Central

    Brown, B. T.; Stafford, Anne; Wright, S. E.

    1962-01-01

    A series of derivatives of digitoxigenin and digoxigenin were prepared and tested for toxicity in the cat and the guinea-pig and on the isolated heart of the 48-hr chick embryo, and for inotropic activity on the cat isolated papillary muscle and the guinea-pig Langendorff heart. The order of relative potency of the compounds remained the same whether they were tested for toxicity or for positive inotropic activity. There are three molecular centres in the cardiac aglycone that are linked closely with cardiac activity. These are: (a) an OH at carbon-3 which can be combined as a glycoside, thus enhancing activity, or esterified or oxidized, producing compounds of lower activity; the maximum intensity of the inotropic response was reduced in the less potent compounds; (b) a 14-β-OH associated with a cis C-D ring junction, alteration of which abolished activity; (c) an unsaturated cyclobutenolide ring which cannot be reduced without a great decrease in activity. PMID:13873586

  15. Chemical Synthesis of a Glycopeptide Derived from Skp1 for Probing Protein Specific Glycosylation.

    PubMed

    Chinoy, Zoeisha S; Schafer, Christopher M; West, Christopher M; Boons, Geert-Jan

    2015-08-10

    Skp1 is a cytoplasmic and nuclear protein, best known as an adaptor of the SCF family of E3-ubiquitin ligases that label proteins for their degradation. Skp1 in Dictyostelium is posttranslationally modified on a specific hydroxyproline (Hyp) residue by a pentasaccharide, which consists of a Fucα1,2-Galβ-1,3-GlcNAcα core, decorated with two α-linked Gal residues. A glycopeptide derived form Skp1 was prepared to characterize the α-galactosyltransferase (AgtA) that mediates the addition of the α-Gal moieties, and to develop antibodies suitable for tracking the trisaccharide isoform of Skp1 in cells. A strategy was developed for the synthesis of the core trisaccharide-Hyp based on the use of 2-naphthylmethyl (Nap) ethers as permanent protecting groups to allow late stage installation of the Hyp moiety. Tuning of glycosyl donor and acceptor reactivities was critical for achieving high yields and anomeric selectivities of glycosylations. The trisaccharide-Hyp moiety was employed for the preparation of the glycopeptide using microwave-assisted solid phase peptide synthesis. Enzyme kinetic studies revealed that trisaccharide-Hyp and trisaccharide-peptide are poorly recognized by AgtA, indicating the importance of context provided by the native Skp1 protein for engagement with the active site. The trisaccharide-peptide was a potent immunogen capable of generating a rabbit antiserum that was highly selective toward the trisaccharide isoform of full-length Skp1. PMID:26179871

  16. Bioprospecting Chemical Diversity and Bioactivity in a Marine Derived Aspergillus terreus.

    PubMed

    Adpressa, Donovon A; Loesgen, Sandra

    2016-02-01

    A comparative metabolomic study of a marine derived fungus (Aspergillus terreus) grown under various culture conditions is presented. The fungus was grown in eleven different culture conditions using solid agar, broth cultures, or grain based media (OSMAC). Multivariate analysis of LC/MS data from the organic extracts revealed drastic differences in the metabolic profiles and guided our subsequent isolation efforts. The compound 7-desmethylcitreoviridin was isolated and identified, and is fully described for the first time. In addition, 16 known fungal metabolites were also isolated and identified. All compounds were elucidated by detailed spectroscopic analysis and tested for antibacterial activities against five human pathogens and tested for cytotoxicity. This study demonstrates that LC/MS based multivariate analysis provides a simple yet powerful tool to analyze the metabolome of a single fungal strain grown under various conditions. This approach allows environmentally-induced changes in metabolite expression to be rapidly visualized, and uses these differences to guide the discovery of new bioactive molecules. PMID:26880440

  17. Practical silicon deposition rules derived from silane monitoring during plasma-enhanced chemical vapor depositiona)

    NASA Astrophysics Data System (ADS)

    Bartlome, Richard; De Wolf, Stefaan; Demaurex, Bénédicte; Ballif, Christophe; Amanatides, Eleftherios; Mataras, Dimitrios

    2015-05-01

    We clarify the difference between the SiH4 consumption efficiency η and the SiH4 depletion fraction D, as measured in the pumping line and the actual reactor of an industrial plasma-enhanced chemical vapor deposition system. In the absence of significant polysilane and powder formation, η is proportional to the film growth rate. Above a certain powder formation threshold, any additional amount of SiH4 consumed translates into increased powder formation rather than into a faster growing Si film. In order to discuss a zero-dimensional analytical model and a two-dimensional numerical model, we measure η as a function of the radio frequency (RF) power density coupled into the plasma, the total gas flow rate, the input SiH4 concentration, and the reactor pressure. The adjunction of a small trimethylboron flow rate increases η and reduces the formation of powder, while the adjunction of a small disilane flow rate decreases η and favors the formation of powder. Unlike η, D is a location-dependent quantity. It is related to the SiH4 concentration in the plasma cp, and to the phase of the growing Si film, whether the substrate is glass or a c-Si wafer. In order to investigate transient effects due to the RF matching, the precoating of reactor walls, or the introduction of a purifier in the gas line, we measure the gas residence time and acquire time-resolved SiH4 density measurements throughout the ignition and the termination of a plasma.

  18. Practical silicon deposition rules derived from silane monitoring during plasma-enhanced chemical vapor deposition

    SciTech Connect

    Bartlome, Richard De Wolf, Stefaan; Demaurex, Bénédicte; Ballif, Christophe; Amanatides, Eleftherios; Mataras, Dimitrios

    2015-05-28

    We clarify the difference between the SiH{sub 4} consumption efficiency η and the SiH{sub 4} depletion fraction D, as measured in the pumping line and the actual reactor of an industrial plasma-enhanced chemical vapor deposition system. In the absence of significant polysilane and powder formation, η is proportional to the film growth rate. Above a certain powder formation threshold, any additional amount of SiH{sub 4} consumed translates into increased powder formation rather than into a faster growing Si film. In order to discuss a zero-dimensional analytical model and a two-dimensional numerical model, we measure η as a function of the radio frequency (RF) power density coupled into the plasma, the total gas flow rate, the input SiH{sub 4} concentration, and the reactor pressure. The adjunction of a small trimethylboron flow rate increases η and reduces the formation of powder, while the adjunction of a small disilane flow rate decreases η and favors the formation of powder. Unlike η, D is a location-dependent quantity. It is related to the SiH{sub 4} concentration in the plasma c{sub p}, and to the phase of the growing Si film, whether the substrate is glass or a c-Si wafer. In order to investigate transient effects due to the RF matching, the precoating of reactor walls, or the introduction of a purifier in the gas line, we measure the gas residence time and acquire time-resolved SiH{sub 4} density measurements throughout the ignition and the termination of a plasma.

  19. Microstructural, Chemical and Mechanical Characterization of Polymer-Derived Hi-Nicalon Fibers with Surface Coatings

    NASA Technical Reports Server (NTRS)

    Bansal, Narottam P.; Chen, Yuan L.

    1998-01-01

    Room temperature tensile strengths of as-received Hi-Nicalon fibers and those having BN/SiC, p-BN/SiC, and p-B(Si)N/SiC surface coatings, deposited by chemical vapor deposition, were measured using an average fiber diameter of 13.5 microns. The Weibull statistical parameters were determined for each fiber. The average tensile strength of uncoated Hi-Nicalon on was 3.19 +/- 0.73 GPa with a Weibull modulus of 5.41. Strength of fibers coated with BN/SiC did not change. However, coat with p-BN/SiC and p-B(Si)N/SiC surface layers showed strength loss of approx. 10 and 35 percent, respectively, compared with as-received fibers. The elemental compositions of the fibers and the coatings were analyzed using scanning Auger microprobe and energy dispersive x-ray spectroscopy. The BN coating was contaminated with a large concentration of carbon and some oxygen. In contrast, p-BN, p-B(Si)N, and SiC coatings did not show any contamination. Microstructural analyses of the fibers and the coatings were done by scanning electron microscopy (SEM), transmission electron microscopy (TEM), and selected area electron diffraction. Hi-Nicalon fiber consists of the P-SIC nanocrystals ranging in size from 1 to 30 nm embedded in an amorphous matrix. TEM analysis of the BN coating revealed four distinct layers with turbostatic structure. The p-BN layer was turbostratic and showed considerable preferred orientation. The p-B(Si)N was glassy and the silicon and boron were uniformly distributed. The silicon carbide coating was polycrystalline with a columnar structure along the growth direction. The p-B(Si)N/SiC coatings were more uniform, less defective and of better quality than the BN/SiC or the p-BN/SiC coatings.

  20. Surfaces for immobilization of N-terminal cysteine derivatives via native chemical ligation.

    PubMed

    Anderson, Sally

    2008-12-16

    This paper presents an improved method for fast, reliable, and quantitative native chemical ligation (NCL--the reaction between an N-terminal cysteine and a thioester to yield an amide bond) at thiophenyl ester-functionalized glass surfaces. For the first time, the degree of surface functionalization has been measured and can be readily controlled by varying the concentration of thiophenyl ester groups on the surface. This methodology facilitates the preparation of tailor-made functionalized glass surfaces for diverse applications. S-Phenyl 11-(chlorodimethylsilyl)-undecanethiolate, and the benzyl analogue, are readily prepared from 10-undecanoic acid via thioester formation and platinum-catalyzed hydrosilylation of the terminal alkene functionality. Thioesters covalently bound to glass surfaces were then formed by submerging clean glass in toluene-solutions of the relevant thioester silylchloride (1%) containing the non-nucleophilic base, ethyldiisopropylamine (1%). NCL was explored with a cysteine-lissamine conjugate, and the degree of surface functionalization was quantified by UV/vis absorption spectroscopy, using the lissamine chromophore. NCL at thiophenyl ester surfaces proved fast (half-life less than 10 min) and yielded levels of surface functionalization consistent with a dense monolayer of dimethyloctylsilane (ca. 2.0 molecules/nm2). Water contact angles on thiophenyl ester surfaces were found to decrease after NCL reaction with the cysteine-lissamine conjugate, whereas surfaces treated with the same buffer solution containing an unreactive alanine-lissamine conjugate showed no significant changes in contact angle, indicating that thioester hydrolysis is not significant during the course of the reaction. NCL with the cysteine-lissamine conjugate at mixed surfaces containing both thiophenyl esters and inert octyl chains showed lower levels of surface functionalization as expected. Plotting the proportion of thiophenyl esters used in the preparation of the substrates against integrated absorption from the surface yielded a linear relationship, demonstrating that NCL on these surfaces occurs in a controllable manner. PMID:19360954

  1. Chemical-looping combustion of coal-derived synthesis gas over copper oxide oxygen carriers

    SciTech Connect

    Tian, H.; Chaudhari, K.; Simonyi, T.; Poston, J.; Liu, T.; Sanders, T.; Veser, G.; Siriwardane, R.

    2008-01-01

    CuO/bentonite and CuO-BHA nanocomposites were studied as oxygen carriers in chemical-looping combustion (CLC) of simulated synthesis gas. Global reaction rates of reduction and oxidation, as the function of reaction conversion, were calculated from 10-cycle oxidation/reduction tests utilizing thermogravimetric analysis at atmospheric pressure between 700 and 900 °C. It was found that the reduction reactions are always faster than oxidation reactions; reaction temperature and particle size do not significantly affect the reaction performance of CuO/bentonite. Multicycle CLC tests conducted in a high-pressure flow reactor showed stable reactivity for production of CO2 from fuel gas at 800 and 900 °C and full consumption of hydrogen during the reaction. Results of the tapered element oscillating microbalance showed a negative effect of pressure on the global rates of reduction-oxidation reactions at higher fractional conversions. X-ray diffraction patterns confirmed the presence of CuO in the bulk phase of the oxidized sample. Electron microanalysis showed significant morphology changes of reacted CuO/bentonite samples after the 10 oxidation-reduction cycles above 700 °C in an atmospheric thermogravimetric analyzer. The nanostructured CuO-BHA carrier also showed excellent stability and, in comparison to the CuO/bentonite system, slightly accelerated redox kinetics albeit at the expense of significantly increased complexity of manufacturing. Overall, both types of CuO carriers exhibited excellent reaction performance and thermal stability for the CLC process at 700-900 °C.

  2. Chemical-looping Combustion of Coal-derived Synthesis Gas Over Copper Oxide Oxygen Carriers

    SciTech Connect

    Tian, Hanjing; Chaudhari, K P; Simonyi, Thomas; Poston, J A; Liu, Tengfei; Sanders, Tom; Veser, Goetz; Siriwardane, R V

    2008-11-01

    CuO/bentonite and CuO-BHA nanocomposites were studied as oxygen carriers in chemical-looping combustion (CLC) of simulated synthesis gas. Global reaction rates of reduction and oxidation, as the function of reaction conversion, were calculated from 10-cycle oxidation/reduction tests utilizing thermogravimetric analysis at atmospheric pressure between 700 and 900 °C. It was found that the reduction reactions are always faster than oxidation reactions; reaction temperature and particle size do not significantly affect the reaction performance of CuO/bentonite. Multicycle CLC tests conducted in a high-pressure flow reactor showed stable reactivity for production of CO2 from fuel gas at 800 and 900 °C and full consumption of hydrogen during the reaction. Results of the tapered element oscillating microbalance showed a negative effect of pressure on the global rates of reduction-oxidation reactions at higher fractional conversions. X-ray diffraction patterns confirmed the presence of CuO in the bulk phase of the oxidized sample. Electron microanalysis showed significant morphology changes of reacted CuO/bentonite samples after the 10 oxidation-reduction cycles above 700 °C in an atmospheric thermogravimetric analyzer. The nanostructured CuO-BHA carrier also showed excellent stability and, in comparison to the CuO/bentonite system, slightly accelerated redox kinetics albeit at the expense of significantly increased complexity of manufacturing. Overall, both types of CuO carriers exhibited excellent reaction performance and thermal stability for the CLC process at 700-900 °C.

  3. Chemical-looping combustion of coal-derived synthesis gas over copper oxide oxygen carriers

    SciTech Connect

    Hanjing Tian; Karuna Chaudhari; Thomas Simonyi; James Poston; Tengfei Liu; Tom Sanders; Goetz Veser; Ranjani Siriwardane

    2008-11-15

    CuO/bentonite and CuO-BHA nanocomposites were studied as oxygen carriers in chemical-looping combustion (CLC) of simulated synthesis gas. Global reaction rates of reduction and oxidation, as the function of reaction conversion, were calculated from 10-cycle oxidation/reduction tests utilizing thermogravimetric analysis at atmospheric pressure between 700 and 900{degree}C. It was found that the reduction reactions are always faster than oxidation reactions; reaction temperature and particle size do not significantly affect the reaction performance of CuO/bentonite. Multicycle CLC tests conducted in a high-pressure flow reactor showed stable reactivity for production of CO{sub 2} from fuel gas at 800 and 900{degree}C and full consumption of hydrogen during the reaction. Results of the tapered element oscillating microbalance showed a negative effect of pressure on the global rates of reduction-oxidation reactions at higher fractional conversions. X-ray diffraction patterns confirmed the presence of CuO in the bulk phase of the oxidized sample. Electron microanalysis showed significant morphology changes of reacted CuO/bentonite samples after the 10 oxidation-reduction cycles above 700{degree}C in an atmospheric thermogravimetric analyzer. The nanostructured CuO-BHA carrier also showed excellent stability and, in comparison to the CuO/bentonite system, slightly accelerated redox kinetics albeit at the expense of significantly increased complexity of manufacturing. Overall, both types of CuO carriers exhibited excellent reaction performance and thermal stability for the CLC process at 700-900{degree}C. 48 refs., 12 figs., 8 tabs.

  4. Inhibition of chemically-induced neoplastic transformation by a novel tetrasodium diphosphate astaxanthin derivative.

    PubMed

    Hix, Laura M; Frey, Dean A; McLaws, Mark D; Østerlie, Marianne; Lockwood, Samuel F; Bertram, John S

    2005-09-01

    Carotenoids have been implicated in numerous epidemiological studies as being protective against cancer at many sites, and their chemopreventive properties have been confirmed in laboratory studies. Astaxanthin (AST), primarily a carotenoid of marine origin, responsible for the pink coloration of salmon, shrimp and lobster, has received relatively little attention. As with other carotenoids, its highly lipophilic properties complicate delivery to model systems. To overcome this issue we have synthesized a novel tetrasodium diphosphate astaxanthin (pAST) derivative with aqueous dispersibility of 25.21 mg/ml. pAST was delivered to C3H/10T1/2 cells in an aqueous/ethanol solution and compared with non-esterified AST dissolved in tetrahydrofuran. We show pAST to (i) upregulate connexin 43 (Cx43) protein expression; (ii) increase the formation of Cx43 immunoreactive plaques; (iii) upregulate gap junctional intercellular communication (GJIC); and (iv) cause 100% inhibition of methylcholanthrene-induced neoplastic transformation at 10(-6) M. In all these assays, pAST was superior to non-esterified AST itself; in fact, pAST exceeded the potency of all other previously tested carotenoids in this model system. Cleavage of pAST to non-esterified (free) AST and uptake into cells was also verified by HPLC; however, levels of free AST were approximately 100-fold lower than in cells treated with AST itself, suggesting that pAST possesses intrinsic activity. The dual properties of water dispersibility (enabling parenteral administration in vivo) and increased potency should prove extremely useful in the future development of cancer chemopreventive agents. PMID:15888493

  5. Amphiphilic 1-deoxynojirimycin derivatives through click strategies for chemical chaperoning in N370S Gaucher cells.

    PubMed

    Diot, Jennifer D; Garcia Moreno, Isabel; Twigg, Gabriele; Ortiz Mellet, Carmen; Haupt, Karsten; Butters, Terry D; Kovensky, José; Gouin, Sébastien G

    2011-10-01

    In Gaucher disease (GD), mutant β-glucocerebrosidases (β-GCase) that are misfolded are recognized by the quality control machinery of the endoplasmic reticulum (ER) and degraded proteolytically. Hydrophobic iminosugars can be used as pharmacological chaperones to provide an improvement in the folding of the enzyme and promote trafficking from the ER. We have developed here an efficient click procedure to tether hydrophobic substituents to N-azidopropyl-1-deoxynojirimycin. A set of 14 original iminosugars was designed and evaluated for inhibition of commercially available glucosidases. Most of the compounds were micromolar inhibitors of those enzymes. In vitro inhibition assays with the N370S β-GCase revealed that the sublibrary containing the derivatives with aromatic aglycons displayed the highest inhibitory potency. Chaperone activity of the whole set of synthetic compounds was also explored in mutant Gaucher cells. The most active compound gave a nearly 2-fold increase in enzyme activity at 20 μM, a significantly higher value than the 1.33-fold recorded for the reference compound N-nonyl-1-deoxynojirimycin (N-nonyl-DNJ). As previously reported with bicyclic sp(2)-iminosugars (Luan, Z.; Higaki, K.; Aguilar-Moncayo, M.; Ninomiya, H.; Ohno, K.; García-Moreno, M. I.; Ortiz Mellet, C.; García Fernández, J. M.; Suzuki, Y. ChemBioChem 2009, 10, 2780), in vitro inhibition of β-GCase measured for the compounds did not correlate with the cellular chaperone activity. The potency of new iminosugar chaperones is therefore not predictable from structure-activity relationships studies based on the in vitro β-GCase inhibition. PMID:21830816

  6. Quantum chemical and experimental studies on the mechanism of alkylation of beta-dicarbonyl compounds. The synthesis of five and six membered heterocyclic spiro derivatives.

    PubMed

    Sadikov, Nurettin; Nasibov, Sahin; Oğretir, Cemil; Berber, Halil; Hüseyinli, Ali

    2004-01-01

    The alkylation of beta-dicarbonyl compounds in a K2CO3/DMSO system was found to afford O- and C-alkylated derivatives, depending on the type of the beta-dicarbonyl compound involved. The alkyl derivatives obtained were used in the synthesis of some new spiro barbituric acid derivatives. Quantum chemical calculations were carried out to elucidate the reaction mechanisms for some typical synthesis. PMID:18007493

  7. Theoretical predictions of chemical degradation reaction mechanisms of RDX and other cyclic nitramines derived from their molecular structures.

    PubMed

    Qasim, M; Fredrickson, H; McGrath, C; Furey, J; Bajpai, R

    2005-06-01

    Analysis of environmental degradation pathways of contaminants is aided by predictions of likely reaction mechanisms and intermediate products derived from computational models of molecular structure. Quantum mechanical methods and force-field molecular mechanics were used to characterize cyclic nitramines. Likely degradation mechanisms for hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) include hydroxylation utilizing addition of hydroxide ions to initiate proton abstraction via 2nd order rate elimination (E2) or via nucleophilic substitution of nitro groups, reductive chemical and biochemical degradation, and free radical oxidation. Due to structural similarities, it is predicted that, under homologous circumstances, certain RDX environmental degradation pathways should also be effective for octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) and similar cyclic nitramines. Computational models provided a theoretical framework whereby likely transformation mechanisms and transformation products of cyclic nitramines were predicted and used to elucidate in situ degradation pathways. PMID:15804809

  8. Impact of climate and parent material on chemical weathering in Loess-derived soils of the Mississippi River valley

    USGS Publications Warehouse

    Muhs, D.R.; Bettis, E. Arthur, III; Been, J.; McGeehin, J.P.

    2001-01-01

    Peoria Loess-derived soils on uplands east of the Mississippi River valley were studied from Louisiana to Iowa, along a south-to-north gradient of decreasing precipitation and temperature. Major element analyses of deep loess in Mississippi and Illinois show that the composition of the parent material is similar in the northern and southern parts of the valley. We hypothesized that in the warmer, wetter parts of the transect, mineral weathering should be greater than in the cooler, drier parts of the transect. Profile average values of CaO/TiO2, MgO/ TiO2, K2O/TiO2, and Na2O/TiO2, Sr/Zr, Ba/Zr, and Rb/Zr represent proxies for depletion of loess minerals such as calcite, dolomite, hornblende, mica, and plagioclase. All ratios show increases from south to north, supporting the hypothesis of greater chemical weathering in the southern part of the valley. An unexpected result is that profile average values of Al2O3/TiO2 and Fe2O3/TiO2 (proxies for the relative abundance of clay minerals) show increases from south to north. This finding, while contrary to the evidence of greater chemical weathering in the southern part of the transect, is consistent with an earlier study which showed higher clay contents in Bt horizons of loess-derived soils in the northern part of the transect. We hypothesize that soils in the northern part of the valley received fine-grained loess from sources to the west of the Mississippi River valley either late in the last glacial period, during the Holocene or both. In contrast, soils in the southern part of the valley were unaffected by such additions.

  9. Synthesis and Antidiabetic Evaluation of Benzenesulfonamide Derivatives

    PubMed Central

    Hosseinzadeh, Nouraddin; Seraj, Soodeh; Bakhshi-Dezffoli, Mohamad Ebrahim; Hasani, Mohammad; Khoshneviszadeh, Mehdi; Fallah-Bonekohal, Saeed; Abdollahi, Mohammad; Foroumadi, Alireza; Shafiee, Abbas

    2013-01-01

    The complex metabolic syndrome, diabetes mellitus, is a major human health concern in the world and is estimated to affect 300 million people by the year 2025. Several drugs such as sulfonylureas and biguanides are presently available to reduce hyperglycemia in diabetes mellitus. These drugs have side effects and thus searching for a new class of compounds is essential to overcome this problems. A series of seven novel N-(4-phenylthiazol-2-yl)benzenesulfonamides derivatives were synthesized and assayed in-vivo to investigate their antidiabetic activities by streptozotocin-induced model in rat. These derivatives showed considerable biological efficacy when compared to glibenclamide, a potent and well-known antidiabetic agent, as a reference drug. Four of the compounds were effective, amongst which 13 show more prominent activity at 100 mg/Kg p.o. The experimental results are statistically significant at p < 0.05 level. PMID:24250607

  10. Molecular dynamics simulation and quantum chemical calculations for the adsorption of some Azo-azomethine derivatives on mild steel

    NASA Astrophysics Data System (ADS)

    Shokry, H.

    2014-02-01

    The adsorption mechanism and inhibition performance of some Azo-azomethine derivatives [2-hydroxyphenylazo-2‧,4‧-dihydroxy-3‧-formylbenzene(Azo-1), 2-carboxyphenylazo-2‧,4‧-dihydroxy-3‧-formylbenzene (Azo-II), 2-hydroxyphenylazo-2‧,4‧-dihydroxy-3‧-{2-hydroxyphenylazomethine}(Azo-I-azomethine I) and 2-carboxyphenylazo-2‧,4‧-dihydroxy-3‧-{2-hydroxyazo methane} (Azo-II-azomethine II) on mild steel at temperatures ranging from 298 K to 333 K have been studied using molecular dynamics (MD) simulation and quantum chemical computational methods. The results obtained revealed that these molecules could effectively adsorb on Fe (0 0 1) surface and the active adsorption sites of these molecules are the nitrogen, oxygen atoms and special negatively charged carbon atoms. All the inhibitors studied had unique corrosion inhibition performance with Azo-II-azomethine II showing the highest inhibition performance at lower temperature ranges from 298 K to 313 K and Azo-II displaying the highest inhibition performance at higher temperature ranges of 323 K and 333 K. Some quantum chemical parameters and the Mulliken charge densities on the optimized structure of inhibitors were calculated using the 6-31∗G basis set method to provide further insight into the mechanism of the corrosion inhibition process. The local reactivity was analyzed through the Fukui function and condensed softness indices in order to know the possible sites of nucleophillic and electrophillic attacks.

  11. Chemical Reactivity of alpha-Pinene-derived Products in the Aqueous Phase: Implications on the Fate of Organic Nitrates

    NASA Astrophysics Data System (ADS)

    Rindelaub, J. D.; Hostetler, M. A.; Lipton, M. A.; Shepson, P. B.

    2014-12-01

    The production of organic nitrates has significant atmospheric importance due to the impact on regional air quality by influencing NOx lifetimes and ozone formation. Additionally, these low volatility compounds readily partition into the particle phase and are important contributors to secondary organic aerosol. Once in the aerosol phase, organic nitrates undergo further chemical reactions that govern their fate in the atmosphere and, consequently, their impact on air quality. Recent research indicates that the presence of water on aerosol particles has a major impact on the reactivity of organic nitrates and that condensed phase hydrolysis leads to the destruction of organic nitrate species, depending on structure. Despite this knowledge, the chemical mechanisms, products, product reactivity and volatility are still uncertain, negatively impacting our understanding of aerosol phase processing and the contribution to air quality. To further understand the atmospheric impact of aerosol phase hydrolysis, we analyzed both condensed phase hydrolysis reactions involving alpha-pinene-derived standards and alpha-pinene photochemical chamber reaction filter samples, using a suite of spectroscopic and mass spectrometric techniques. We were able to measure the pH-dependent hydrolysis rate constants for several types of organic nitrates and identify specific reaction products. The chemistry involved exhibits a strong dependence on pH, providing important mechanistic clues. The results of this study will significantly contribute to our knowledge of aerosol phase chemistry and the impact on regional air quality with respect to the fate of organic nitrate species.

  12. Maternally derived chemical defences are an effective deterrent against some predators of poison frog tadpoles (Oophaga pumilio)

    PubMed Central

    Stynoski, Jennifer L.; Shelton, Georgia; Stynoski, Peter

    2014-01-01

    Parents defend their young in many ways, including provisioning chemical defences. Recent work in a poison frog system offers the first example of an animal that provisions its young with alkaloids after hatching or birth rather than before. But it is not yet known whether maternally derived alkaloids are an effective defence against offspring predators. We identified the predators of Oophaga pumilio tadpoles and conducted laboratory and field choice tests to determine whether predators are deterred by alkaloids in tadpoles. We found that snakes, spiders and beetle larvae are common predators of O. pumilio tadpoles. Snakes were not deterred by alkaloids in tadpoles. However, spiders were less likely to consume mother-fed O. pumilio tadpoles than either alkaloid-free tadpoles of the red-eyed treefrog, Agalychnis callidryas, or alkaloid-free O. pumilio tadpoles that had been hand-fed with A. callidryas eggs. Thus, maternally derived alkaloids reduce the risk of predation for tadpoles, but only against some predators. PMID:24850895

  13. Lethal and mutagenic effects of radiation and chemicals on cultured fish cells derived from the erythrophoroma of goldfish (Carassius auratus).

    PubMed

    Mitani, H

    1983-02-01

    GEM 199 cells derived from an erythrophoroma of goldfish (Carassius auratus), which had a high plating efficiency, were used to investigate the lethal and mutational effects of radiations (UV and gamma-rays) and chemicals (4NQO and MNNG). The cells were more resistant to gamma-rays than mammalian cells and CAF-MM1 cells derived from the normal fin tissue of goldfish. They were also more resistant to UV-irradiation than CAF-MM1 cells. Photoreactivation after UV-irradiation was present in GEM 199 cells for both survival and mutation. The initial shoulder of the survival curve of UV-irradiated cells was reduced greatly by caffeine, suggesting a high activity of the post-replication repair. The spontaneous mutation frequency to ouabain resistance was 1-5 X 10(-6) clones per viable cell. MNNG was effective in inducing ouabain-resistant mutation, while 4NQO and gamma-rays did not induce mutation. PMID:6408467

  14. Maternally derived chemical defences are an effective deterrent against some predators of poison frog tadpoles (Oophaga pumilio).

    PubMed

    Stynoski, Jennifer L; Shelton, Georgia; Stynoski, Peter

    2014-05-01

    Parents defend their young in many ways, including provisioning chemical defences. Recent work in a poison frog system offers the first example of an animal that provisions its young with alkaloids after hatching or birth rather than before. But it is not yet known whether maternally derived alkaloids are an effective defence against offspring predators. We identified the predators of Oophaga pumilio tadpoles and conducted laboratory and field choice tests to determine whether predators are deterred by alkaloids in tadpoles. We found that snakes, spiders and beetle larvae are common predators of O. pumilio tadpoles. Snakes were not deterred by alkaloids in tadpoles. However, spiders were less likely to consume mother-fed O. pumilio tadpoles than either alkaloid-free tadpoles of the red-eyed treefrog, Agalychnis callidryas, or alkaloid-free O. pumilio tadpoles that had been hand-fed with A. callidryas eggs. Thus, maternally derived alkaloids reduce the risk of predation for tadpoles, but only against some predators. PMID:24850895

  15. Chemical stability and in vitro and clinical efficacy of a novel hybrid retinoid derivative, bis-retinamido methylpentane.

    PubMed

    Kim, Ki Hyun; Lim, Dae Gon; Lim, Jun Yeul; Kim, Nam Ah; Park, So-Hyun; Cho, Jin Hun; Shin, Beom Soo; Jeong, Seong Hoon

    2015-11-10

    The anti-aging agent, retinol, has fewer side effects and similar biological activity compared to retinoic acid. However, retinol becomes unstable when exposed to light and heat. A novel hybrid retinoid derivative, bis-retinamido methylpentane (RS-2A), was newly developed to overcome the limitations. This study evaluated the chemical stability of RS-2A under thermal and light conditions by examining degradation profiles, and assessed the in vitro biological activity, cytotoxicity, and clinical efficacy. Chemical stability and degradation profiles were investigated with HPLC and LC-MS. Especially, photo-stability of RS-2A was analyzed under various conditions, such as change of physical state and concentration, different solvents, and various excipients. For analyses of cellular activity and cytotoxicity, human dermal fibroblasts were cultured with RS-2A. To evaluate the safety and efficacy of the compound with the cellular results, RS-2A was applied to women who had moderate to severe wrinkles at the periorbital region. All of the experiments were conducted with retinol as a reference. RS-2A was more stable than retinol to thermal conditions, especially in solution. Both RS-2A and retinol were unstable to light, but RS-2A showed enhanced photo-stability with regard to concentration, more polar solvent, and addition of proper excipients. RS-2A exhibited decreased cytotoxicity and enhanced effects on collagen synthesis compared with retinol. In a clinical study, a 4-week treatment with RS-2A significantly improved the appearance of periorbital wrinkles without any side effects. The results indicate that RS-2A might have potential as an anti-aging agent for cosmeceutical preparations because of its enhanced chemical stability, biological activity, safety, and clinical efficacy. PMID:26325317

  16. Optical absorption measurements and quantum-chemical simulations on 1H-pyrazolo[3,4-b]quinoline derivatives

    NASA Astrophysics Data System (ADS)

    Ko?cie?, E.; Sanetra, J.; Gondek, E.; Danel, A.; Wis?a, A.; Kityk, A. V.

    2003-11-01

    We present the results of experimental studies and quantum chemical simulation (PM3 and AM1 methods) on a new synthesized pyrazolo[3,4-b]quinoline derivatives: 1,4-diphenyl-3-methyl-, 3,4-diphenyl-1-methyl-, 1,3,4-triphenyl-, 1,3-dimethyl-4-phenyl- and 1,3,4-trimethyl-1H-pyrazolo[3,4-b]quinoline. The quantum chemical analysis reveals similarity in the absorption spectra of 1H-pyrazolo[3,4-b]quinoline and 1,3,4-trimethyl-1H-pyrazolo[3,4-b]quinoline which are characterized by four strong absorption bands in the spectral range 200-500 nm. A substitution of the methyl groups by phenyl groups causes substantial changes of the absorption spectra mainly in the spectral range 240-370 nm. We attribute these differences to additional molecular double bounding segments C?C of the substituted phenyl groups i.e., to ??? * transitions. The comparison of measured and calculated absorption spectra by quantum-chemical AM1 method manifests rather good agreement for all compounds in the part regarding the spectral positions of the first oscillator (absorption threshold). At the same time, the measured spectra reveal the considerable broadening practically of all absorption bands. We attribute these discrepancies to a strong solvent effect. By analyzing the charge density distribution we have shown that the most strongest absorption bands in the spectral region 200-270 nm are related with double bonding segments C?N (n?? * transition).

  17. Quinoxaline derivatives as corrosion inhibitors for mild steel in hydrochloric acid medium: Electrochemical and quantum chemical studies

    NASA Astrophysics Data System (ADS)

    Olasunkanmi, Lukman O.; Kabanda, Mwadham M.; Ebenso, Eno E.

    2016-02-01

    The corrosion inhibition potential of four quinoxaline derivatives namely, 1-[3-(4-methylphenyl)-5-(quinoxalin-6-yl)-4,5-dihydropyrazol-1-yl]butan-1-one (Me-4-PQPB), 1-(3-(4-methoxyphenyl)-5-(quinoxalin-6-yl)-4,5-dihydropyrazol-1-yl)butan-1-one (Mt-4-PQPB), 1-[3-(3-methoxyphenyl)-5-(quinoxalin-6-yl)-4,5-dihydropyrazol-1-yl]butan-1-one (Mt-3-PQPB) and 1-[3-(2H-1,3-benzodioxol-5-yl)-5-(quinoxalin-6-yl)-4,5-dihydropyrazol-1-yl]butan-1-one (Oxo-1,3-PQPB) was studied for mild steel corrosion in 1 M HCl solution using electrochemical, spectroscopic techniques and quantum chemical calculations. The results of both potentiodynamic polarization and electrochemical impedance spectroscopic studies revealed that the compounds are mixed-type inhibitors and the order of corrosion inhibition efficiency at 100 ppm is Me-4-PQPB>Mt-3-PQPB>Oxo-1,3-PQPB>Mt-4-PQPB. Fourier transform infrared (FTIR) and ultraviolet-visible (UV-vis) spectroscopic analyses confirmed the presence of chemical interactions between the inhibitors and mild steel surface. The adsorption of the inhibitor molecules on mild steel surface was found to be both physisorption and chemisorption but predominantly chemisorption. The experimental data obey Langmuir adsorption isotherm. Scanning electron microscopy studies revealed the formation of protective films of the inhibitors on mild steel surface. Quantum chemical parameters obtained from density functional theory (DFT) calculations support experimental results.

  18. Roles of Chemical Complexity and Evolutionary Theory in Some Hepatic and Intestinal Enzymatic Systems in Chemical Reproducibility and Clinical Efficiency of Herbal Derivatives

    PubMed Central

    2014-01-01

    Despite the great marketing success, most physicians attribute poor efficacy to herbals. This perception is due to two situations that are an integral part of the herbal topic. The first is the poor phytochemical reproducibility obtained during the production process of herbal extracts, as herbal extracts are not always standardized in the whole manufacturing process, but only in their titer. The second problem is linked to the evolution of important enzymatic systems: cytochromes and ABC proteins. They are both enzyme classes with detoxifying properties and seem to have evolved from the molecular mould provided by active plant substances. During the evolution, as still happens today, polyphenols, saponins, terpenes, and alkaloids were ingested together with food. They do not possess any nutritional value but seem to be provided with a potential pharmacological activity. Cytochromes and ABC proteins, which evolved over time to detoxify food from vegetable chemical “actives,” now seem to limit the action of herbal derivatives. The comprehension of these 2 events may explain the origin of the widespread scepticism of physicians about herbal medicine and suggests that, after correct herbal standardization, use of antagonists of cytochromes and ABC systems will make it possible to recover their pharmacological potential. PMID:24977222

  19. Gene expression signatures in CD34+-progenitor-derived dendritic cells exposed to the chemical contact allergen nickel sulfate

    SciTech Connect

    Schoeters, Elke . E-mail: elke.schoeters@vito.be; Nuijten, Jean-Marie; Heuvel, Rosette L. van den; Nelissen, Inge; Witters, Hilda; Schoeters, Greet E.R.; Tendeloo, Vigor F.I. van; Berneman, Zwi N.; Verheyen, Geert R.

    2006-10-01

    The detection of the sensitizing potential of chemicals is of great importance to industry. A promising in vitro alternative to the currently applied animal assays for sensitization testing makes use of dendritic cells (DCs) that have the capability to process and present antigens to naive T cells and induce their proliferation. Here, we studied changes in gene expression profiles after exposing DCs to the contact allergen nickel sulfate. CD34+-progenitor-derived DCs, initiated from 3 different donors, were exposed to 60 {mu}M nickel sulfate, during 0.5, 1, 3, 6, 12 and 24 h. cDNA microarrays were used to assess the transcriptional activity of about 11,000 genes. Significant changes in the expression of 283 genes were observed; 178 genes were up-regulated and 93 down-regulated. These genes were involved in metabolism, cell structure, immune response, transcription, signal transduction, transport, and apoptosis. No functional information was found for 74 genes. Real-time RT-PCR was used to confirm the microarray results of 12 genes. In addition, 3 DC maturation markers not present on the microarrays (DEC205, DC LAMP and CCR7) were analyzed using real-time RT-PCR and found to be up-regulated at several time points. Our data indicate that a broad range of biological processes is influenced by nickel. Some processes are clearly linked to the immune response and DC maturation, others may indicate a toxic effect of nickel.

  20. Syntheses, spectroscopic investigation and electronic properties of two sulfonamide derivatives: A combined experimental and quantum chemical approach

    NASA Astrophysics Data System (ADS)

    Mahmood, Ayyaz; Akram, Tehmina; de Lima, Edna Barboza

    2016-03-01

    Two sulfonamides derivatives, N-phenethyl-4-methylbenzenesulfonamide (1) and N-(4-hydroxyphenethyl)-4-methylbenzenesulfonamide (2), were successfully synthesized and fully characterized using 1H NMR, 13C NMR, FT-IR spectroscopies and elemental analysis. The molecular and electronic structures of the compounds were further investigated using density functional theory calculation at B3LYP and B3PW91 functionals using 6-311++G(d,p) basis set to provide structural and spectroscopic information and guide spectral assignments. The experimental and simulated 1H NMR, 13C NMR and FT-IR spectra were compared and the accuracy was discussed. The conformational analysis was performed in order to find the most stable molecular structure of the compounds. Molecular quantities such as ionization potential, electron affinity, electronegativity, electrophilicity index and chemical hardness and softness were calculated and used as an additional molecular characteristic to predict the stability of the molecules. Electronic properties such Mullikan atomic charges, HOMO, LUMO and HOMO-LUMO energy gaps and molecular electrostatic potential maps predict the large intramolecular charge transfer within the molecules and significant substitution effects.

  1. Spectrophotometric determination of aminomethylbenzoic acid using sodium 1,2-naphthoquinone-4-sulfonate as the chemical derivative chromogenic reagent

    NASA Astrophysics Data System (ADS)

    Li, Quan-Min; Yang, Zhan-Jun

    2007-03-01

    A new method has been established for the determination of aminomethylbenzoic acid using sodium 1,2-naphthoquinone-4-sulfonate as the chemical derivative chromogenic reagent. This method is based on the formation of a pink compound from the reaction of aminomethylbenzoic acid and sodium 1,2-naphthoquinone-4-sulfonate. The nucleophilic substitution reaction proceeds quantitatively in pH 12.0 buffer solution. The stoichiometric ratio of the reaction, maximum absorption wavelength and the value of ɛ430 were 1:1, 430 nm, and 2.87 × 10 3 L mol -1 cm -1, respectively. Beer's law was obeyed in the range of 0.80-80 mg/L of aminomethylbenzoic acid. The data have been filled to a linear regression equation A = 0.03183 + 0.01658 C (mg/L), with a correlation coefficient of 0.9996. The detection limit is 0.11 mg/L, R.S.D. is 0.54%, and average recovery is over 99.6%. This paper further improves the determination of aminomethylbenzoic acid compared to the previous methods. The kinetic property and reaction mechanism have also been discussed. This proposed method has been successfully applied to the determination of aminomethylbenzoic acid in injection of aminomethylbenzoic acid with satisfactory results.

  2. QUANTITATION OF MONOSACCHARIDE ISOTOPIC ENRICHMENT IN PHYSIOLOGIC FLUIDS BY ELECTRON IONIZATION OR NEGATIVE CHEMICAL IONIZATION GC/MS USING DI-O-ISOPROPYLIDENE DERIVATIVES.

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The aldonitrile pentaacetate and other derivatives lack ions in the electron ionization (EI) spectra possessing an intact hexose structure and thus must be analyzed by chemical ionization GC/MS in order to study multiple isotopomers. We report methods for quantitation of hexose di-O-isopropylidene a...

  3. Calculation of the {sup 13}C NMR chemical shift of ether linkages in lignin derived geopolymers: Constraints on the preservation of lignin primary structure with diagenesis

    SciTech Connect

    Cody, G.D.; Saghi-Szabo, G.

    1999-01-01

    Methodology for the calculation of {sup 13}C NMR shielding on molecular organic fragments, representative of monomers in a type 3 kerogen, is presented. Geometry optimization of each molecular fragment was carried out using Density Functional Theory employing the generalized gradient approximation. NMR shieldings were calculated using the Individual Gauge for Localized orbital Method. Convincing agreement was obtained between calculated and experimentally derived isotropic chemical shielding values over a broad frequency range. Shielding calculations employing the localized orbitals/local origin method resulted in nearly identical results. NMR chemical shift static powder patterns also exhibit excellent agreement with experimental values. These quantum mechanical calculations were applied to determine the extent of lignin primary structure preservation with diagenesis. Specifically, the calculations were used to assess whether inhomogeneous spectral broadening due to both functional group variation and local configurational variability may inhibit the detection of otherwise significant quantities of alkyl-aryl ethers in lignin derived geopolymers. Determination of the chemical-shielding tensor principle axis values reveals a strong correlation between anisotropy and asymmetry with local configuration effects such as dihedral rotation, phenyl group rotation, and bond angle variation. These results indicate that a range of 9 ppm in the isotropic chemical shift can be ascribed to local configuration. Consequently, an upper limit of 5% alkyl-aryl-linkages may go undetected using NMR spectroscopy on lignin-derived geopolymers at the liginite-sub-bituminous transition. It is concluded that the primary structure of lignin does not persist in kerogens even at relatively low thermal maturities.

  4. Geometric, electronic and intrinsic chemical reactivity properties of mono- and bi-substituted quinoline derivatives for the ground state in gas phase

    NASA Astrophysics Data System (ADS)

    Neira Bueno, O. L.; Hincapié H, L.; García Madrid, C.

    2016-02-01

    The study of geometric, electronic properties and intrinsic chemical reactivity is presented for the case of Quinoline and three-derived molecules (4-Amino-Quinoline, 3- Phenyl-Quinoline, 4-Amino-3-phenylquinoline). The study was carried for the ground state in gas phase in the context of the functional theory density using B3LYP/6 31+G (d) model. The purpose of the study is aimed for identifying a compound derived from quinoline, on based to mono- or bi-substitution, using the amino fragment and the phenyl group.

  5. O-Succinyl-L-homoserine-based C4-chemical production: succinic acid, homoserine lactone, γ-butyrolactone, γ-butyrolactone derivatives, and 1,4-butanediol.

    PubMed

    Hong, Kuk-Ki; Kim, Jeong Hyun; Yoon, Jong Hyun; Park, Hye-Min; Choi, Su Jin; Song, Gyu Hyeon; Lee, Jea Chun; Yang, Young-Lyeol; Shin, Hyun Kwan; Kim, Ju Nam; Cho, Kyung Ho; Lee, Jung Ho

    2014-10-01

    There has been a significant global interest to produce bulk chemicals from renewable resources using engineered microorganisms. Large research programs have been launched by academia and industry towards this goal. Particularly, C4 chemicals such as succinic acid (SA) and 1,4-butanediol have been leading the path towards the commercialization of biobased technology with the effort of replacing chemical production. Here we present O-Succinyl-L-homoserine (SH) as a new, potentially important platform biochemical and demonstrate its central role as an intermediate in the production of SA, homoserine lactone (HSL), γ-butyrolactone (GBL) and its derivatives, and 1,4-butanediol (BDO). This technology encompasses (1) the genetic manipulation of Escherichia coli to produce SH with high productivity, (2) hydrolysis into SA and homoserine (HS) or homoserine lactone hydrochloride, and (3) chemical conversion of either HS or homoserine lactone HCL (HSL·HCl) into drop-in chemicals in polymer industry. This production strategy with environmental benefits is discussed in the perspective of targeting of fermented product and a process direction compared to petroleum-based chemical conversion, which may reduce the overall manufacturing cost. PMID:25155257

  6. Production of a refined biooil derived by fast pyrolysis of chicken manure with chemical and physical characteristics close to those of fossil fuels.

    PubMed

    Monreal, Carlos M; Schnitzer, Morris

    2011-01-01

    The chemical and physical properties of raw biooils prevent their direct use in combustion engines. We processed raw pyrolytic biooil derived from chicken manure to yield a colorless refined biooil with diesel qualities. Chemical characterization of the refined biooil involved elemental and several spectroscopic analyses. The physical measurements employed were viscosity, density and heat of combustion. The elemental composition (% wt/wt) of the refined biooil was 82.7 % C, 15.3 % H, 0.2 % N and 1.8 % O, no S. Its viscosity was 0.006 Pa.s and a heat of combustion of 43 MJ kg(-1). The refined biooil fraction contains n-alkanes, ranging from n-C(14) to n-C(27), alkenes varying from C(10:1) to C(22:1), and long-chain alcohols. The refined biooil makes a good diesel fuel due to its chemical and physical properties. PMID:21749251

  7. Organic reactions for the electrochemical and photochemical production of chemical fuels from CO2--The reduction chemistry of carboxylic acids and derivatives as bent CO2 surrogates.

    PubMed

    Luca, Oana R; Fenwick, Aidan Q

    2015-11-01

    The present review covers organic transformations involved in the reduction of CO2 to chemical fuels. In particular, we focus on reactions of CO2 with organic molecules to yield carboxylic acid derivatives as a first step in CO2 reduction reaction sequences. These biomimetic initial steps create opportunities for tandem electrochemical/chemical reductions. We draw parallels between long-standing knowledge of CO2 reactivity from organic chemistry, organocatalysis, surface science and electrocatalysis. We point out some possible non-faradaic chemical reactions that may contribute to product distributions in the production of solar fuels from CO2. These reactions may be accelerated by thermal effects such as resistive heating and illumination. PMID:26022364

  8. Determination of oxygen and nitrogen derivatives of polycyclic aromatic hydrocarbons in fractions of asphalt mixtures using liquid chromatography coupled to mass spectrometry with atmospheric pressure chemical ionization.

    PubMed

    Nascimento, Paulo Cicero; Gobo, Luciana Assis; Bohrer, Denise; Carvalho, Leandro Machado; Cravo, Margareth Coutinho; Leite, Leni Figueiredo Mathias

    2015-12-01

    Liquid chromatography coupled to mass spectrometry with atmospheric pressure chemical ionization was used for the determination of polycyclic aromatic hydrocarbon derivatives, the oxygenated polycyclic aromatic hydrocarbons and nitrated polycyclic aromatic hydrocarbons, formed in asphalt fractions. Two different methods have been developed for the determination of five oxygenated and seven nitrated polycyclic aromatic hydrocarbons that are characterized by having two or more condensed aromatic rings and present mutagenic and carcinogenic properties. The parameters of the atmospheric pressure chemical ionization interface were optimized to obtain the highest possible sensitivity for all compounds. The detection limits of the methods ranged from 0.1 to 57.3 μg/L for nitrated and from 0.1 to 6.6 μg/L for oxygenated derivatives. The limits of quantification were in the range of 4.6-191 μg/L for nitrated and 0.3-8.9 μg/L for oxygenated derivatives. The methods were validated against a diesel particulate extract standard reference material (National Institute of Standards and Technology SRM 1975), and the obtained concentrations (two nitrated derivatives) agreed with the certified values. The methods were applied in the analysis of asphalt samples after their fractionation into asphaltenes and maltenes, according to American Society for Testing and Material D4124, where the maltenic fraction was further separated into its basic, acidic, and neutral parts following the method of Green. Only two nitrated derivatives were found in the asphalt sample, quinoline and 2-nitrofluorene, with concentrations of 9.26 and 2146 mg/kg, respectively, whereas no oxygenated derivatives were detected. PMID:26446274

  9. Minocycline and doxycycline, but not other tetracycline-derived compounds, protect liver cells from chemical hypoxia and ischemia/reperfusion injury by inhibition of the mitochondrial calcium uniporter

    SciTech Connect

    Schwartz, Justin; Holmuhamedov, Ekhson; Zhang, Xun; Lovelace, Gregory L.; Smith, Charles D.; Lemasters, John J.

    2013-11-15

    Minocycline, a tetracycline-derived compound, mitigates damage caused by ischemia/reperfusion (I/R) injury. Here, 19 tetracycline-derived compounds were screened in comparison to minocycline for their ability to protect hepatocytes against damage from chemical hypoxia and I/R injury. Cultured rat hepatocytes were incubated with 50 μM of each tetracycline-derived compound 20 min prior to exposure to 500 μM iodoacetic acid plus 1 mM KCN (chemical hypoxia). In other experiments, hepatocytes were incubated in anoxic Krebs–Ringer–HEPES buffer at pH 6.2 for 4 h prior to reoxygenation at pH 7.4 (simulated I/R). Tetracycline-derived compounds were added 20 min prior to reperfusion. Ca{sup 2+} uptake was measured in isolated rat liver mitochondria incubated with Fluo-5N. Cell killing after 120 min of chemical hypoxia measured by propidium iodide (PI) fluorometry was 87%, which decreased to 28% and 42% with minocycline and doxycycline, respectively. After I/R, cell killing at 120 min decreased from 79% with vehicle to 43% and 49% with minocycline and doxycycline. No other tested compound decreased killing. Minocycline and doxycycline also inhibited mitochondrial Ca{sup 2+} uptake and suppressed the Ca{sup 2+}-induced mitochondrial permeability transition (MPT), the penultimate cause of cell death in reperfusion injury. Ru360, a specific inhibitor of the mitochondrial calcium uniporter (MCU), also decreased cell killing after hypoxia and I/R and blocked mitochondrial Ca{sup 2+} uptake and the MPT. Other proposed mechanisms, including mitochondrial depolarization and matrix metalloprotease inhibition, could not account for cytoprotection. Taken together, these results indicate that minocycline and doxycycline are cytoprotective by way of inhibition of MCU. - Highlights: • Minocycline and doxycycline are the only cytoprotective tetracyclines of those tested • Cytoprotective tetracyclines inhibit the MPT and mitochondrial calcium and iron uptake. • Cytoprotective tetracyclines protect by inhibiting the MCU.

  10. On the toxic effects of tetraethyl lead and its derivatives on the chrysophyte Poterioochromonas malhamensis. III. Chemical analysis

    SciTech Connect

    Roderer, G.

    1981-01-01

    The photolytic decomposition of tetraethyl lead (TEL) into the derivatives triethyl lead (TriEL), diethyl lead (DiEL), and into inorganic lead in an aqueous environment was examined by using a single-step dithizone extraction method. The results of the experiments conclusively indicated that TriEL is the toxic derivative of TEL which is created upon illumination and causes severe inhibitory effects in cultures of Poterioochromonas malhamensis poisoned by TEL. The significance of these findings for polluted natural environments and for the metabolic pathway of organolead in intoxicated mammalia is discussed briefly, and a diagrammatical model is presented describing the presumed fate of TEL and its derivatives under experimental conditions. (JMT)

  11. Design, synthesis, characterization, quantum-chemical calculations and anti-inflammatory activity of novel series of thiophene derivatives

    NASA Astrophysics Data System (ADS)

    Helal, M. H.; Salem, M. A.; Gouda, M. A.; Ahmed, N. S.; El-Sherif, A. A.

    2015-08-01

    Interaction of 1-(4-morpholinophenyl)ethanone 1 with either malononitrile or ethyl cyanoacetate 2 afforded Knoevenagel-Cope product 3. In subsequent treatment of 3 with sulfur, the 2-aminothiophene derivatives (4a, 4b) are formed under basic conditions. The solvent-free reaction of thiophene derivative 4a with ethyl cyanoacetate afforded thieno[2,3-d][1,3]oxazine derivative 6. The base catalyzed condensation of 2-aminothiophene derivative (4a) with ethyl cyanoacetate afforded N-(thieno-2-yl) cyanoacetamide derivative 7. The latter was used to synthesize different heterocyclic derivatives comprising, pyridine and coumarin rings. Also, several substituted thieno[2,3-d]pyrimidines have been prepared from reaction of 2-aminothiophene-3-carbonitrile 4b with some electrophilic reagents. The structure of the newly compounds were confirmed on the basis of elemental analysis and spectral data. The molecular modeling of the synthesized compounds has been drawn and their molecular parameters were calculated. Also, valuable information is obtained from calculation of the molecular parameters including electronegativity, net dipole moment of the compounds, total energy, electronic energy, binding energy, HOMO and LUMO energy. Evaluation of anti-inflammatory activity of the tested compounds was performed in albino rats by producing carrageenan induced paw oedema and measuring the zone of inflammation at different time intervals i.e. 1, 2, 3 and 4 h after carrageenan injection. Results indicated that most of the tested compounds showed moderate to good activity comparable to indomethacin. Also, compound 16 with additional morpholine ring beside the thiophene ring inhibits carrageenan induced paw oedema more than the standard indomethacin drug at all the time scales studied. Thus, compound 16 is considered as a promising compound for further modification to obtain clinically useful anti-inflammatory agent.

  12. Identification of volatile/semivolatile products derived from chemical remediation of cis-1,3-dichloropropene by thiosulfate

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The prevalent use of soil fumigants resulted in air pollution in some agricultural regions. Our previous research showed that application of thiosulfate fertilizers at the soil surface may offer an effective and economical approach to reduce the emission of halogenated fumigants via a chemical remed...

  13. Derivation of Tissue-specific Functional Gene Sets to Aid Transcriptomic Analysis of Chemical Impacts on the Teleost Reproductive Axis.

    EPA Science Inventory

    Oligonucleotide microarrays are a powerful tool for unsupervised analysis of chemical impacts on biological systems. However, the lack of well annotated biological pathways for many aquatic organisms, including fish, and the poor power of microarray-based analyses to detect diffe...

  14. Dual photonic-bandgap optical films towards the generation of photonic crystal-derived 2-dimensional chemical codes.

    PubMed

    Zhang, Jing; Yang, Shengyang; Tian, Yu; Wang, Cai-Feng; Chen, Su

    2015-07-01

    Chemical-oriented 2-dimensional (2D) optical codes were constructed for the first time by integrating bi-layer or bistriate-structure responsive photonic crystals (RPCs), which not only presents high information capacity in encoding processes, but offers a facile route to the detection of high performance sensors along with accurate analysis and anti-jamming performances. PMID:26036800

  15. INFLUENCE OF DECOMPOSITION ON CHEMICAL PROPERTIES OF PLANT-AND MANURE-DERIVED DISSOLVED ORGANIC MATTER AND SORPTION TO GOETHITE

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Sorption of dissolved organic matter (DOM) plays an important role in maintaining the fertility and quality of soils in agricultural ecosystems. Few studies have examined the effects of decomposition on DOM sorption and chemical characteristics. This study investigated the sorption to goethite of ...

  16. Identification of Volatile/Semi-Volatile Products Derived from Chemical Remediation of cis-1,3-Dichloropropene by Thiosulfate

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The prevalent use of soil fumigants has resulted in air pollution in some agricultural regions. Our previous research showed that amendment of thiosulfate fertilizers at the soil surface may offer an effective and economical approach to reduce the emission of halogenated fumigants via a chemical rem...

  17. Chemical characterization of DNA adducts derived from the configurationally isomeric benzo(c)phenanthrene 3,4-diol-1,2-epoxides

    SciTech Connect

    Agarwal, S.K.; Sayer, J.M.; Yeh, H.J.C.; Yagi, H.; Hilton, B.D.; Pigott, M.A.; Dipple, A.; Jerina, D.M.

    1986-05-01

    Upon reaction in vitro with calf thymus DNA, the two pairs of enantiomeric benzo(c)phenanthrene 3,4-diol-1,2-epoxides (in which the epoxide oxygen is either cis or trans to the benzylic hydroxyl group) derived from the enantiomeric benzo(c)phenanthrene trans-3,4-dihydrodiols have previously been shown to bind covalently to deoxyguanosine and deoxyadenosine residues with exceptionally high efficiency relative to epoxide hydrolysis. In order to identify the chemical structures of the adducts formed (one cis and one trans addition product derived from the reaction of each of the four configurationally isomeric diol epoxides with either deoxyguanosine or deoxyadenosine), these adducts have been prepared and compared to the adducts derived from DNA. The stereochemistry (cis or trans addition to the epoxide) for each adduct was deduced from the /sup 1/H-NMR spectrum of its pentaacetate ester. A combination of NMR spectroscopy, chemical stability considerations and pH titration established the site of substitution as the exocyclic nitrogen of guanine or adenine. A correlation was observed between R-absolute configuration at C/sub 1/ of the benzo(c)phenanthrene moiety and negative ellipticity for the major CD band (approx.250-260 nm) exhibited by these adducts.

  18. mTOR inhibitors and the anti-diabetic biguanide metformin: new insights into the molecular management of breast cancer resistance to the HER2 tyrosine kinase inhibitor lapatinib (Tykerb).

    PubMed

    Vázquez-Martín, Alejandro; Oliveras-Ferraros, Cristina; del Barco, Sonia; Martín-Castillo, Begoña; Menéndez, Javier A

    2009-07-01

    The small molecule HER2 tyrosine kinase inhibitor (TKI) lapatinib (Tykerb) is approved for the therapy of patients with HER2-positive breast carcinomas who have progressed on trastuzumab (Herceptin). Unfortunately, the efficacy of this HER2 TKI is limited by both primary (inherent) and acquired resistance, the latter typically occurring within 12 months of starting therapy. One of the key factors limiting our understanding of the mechanisms involved in lapatinib resistance is the lack of published preclinical models. We herein review lapatinib-refractory models recently developed at the bench and the survival pathways discovered. As hyperactivation of the pharmacologically targetable PI3K/mTOR/p70S6K1 axis appears to be central to the occurrence of lapatinib resistance, preclinical data showing enhanced antitumour effects when combining lapatinib with mTOR inhibitors (e.g., rapamycin analogues and NVP-BEZ235) highlight the importance of translational work to yield clinically useful regimens capable of delaying or treating lapatinib resistance. The unexpected ability of the anti-type II diabetes drug metformin to inactivate mTOR and decrease p70S6K1 activity further reveals that this biguanide, generally considered non-toxic and remarkably inexpensive, might be considered for new combinatorial lapatinib-based protocols in HER2-overexpressing breast cancer patients. PMID:19574203

  19. Genomic and chemical insights into biosurfactant production by the mangrove-derived strain Bacillus safensis CCMA-560.

    PubMed

    Domingos, Daniela Ferreira; de Faria, Andreia Fonseca; de Souza Galaverna, Renan; Eberlin, Marcos Nogueira; Greenfield, Paul; Zucchi, Tiago Domingues; Melo, Itamar Soares; Tran-Dinh, Nai; Midgley, David; de Oliveira, Valéria Maia

    2015-04-01

    Many Bacillus species can produce biosurfactant, although most of the studies on lipopeptide production by this genus have been focused on Bacillus subtilis. Surfactants are broadly used in pharmaceutical, food and petroleum industry, and biological surfactant shows some advantages over the chemical surfactants, such as less toxicity, production from renewable, cheaper feedstocks and development of novel recombinant hyperproducer strains. This study is aimed to unveil the biosurfactant metabolic pathway and chemical composition in Bacillus safensis strain CCMA-560. The whole genome of the CCMA-560 strain was previously sequenced, and with the aid of bioinformatics tools, its biosurfactant metabolic pathway was compared to other pathways of closely related species. Fourier transform infrared (FTIR) and high-resolution TOF mass spectrometry (MS) were used to characterize the biosurfactant molecule. B. safensis CCMA-560 metabolic pathway is similar to other Bacillus species; however, some differences in amino acid incorporation were observed, and chemical analyses corroborated the genetic results. The strain CCMA-560 harbours two genes flanked by srfAC and srfAD not present in other Bacillus spp., which can be involved in the production of the analogue gramicidin. FTIR and MS showed that B. safensis CCMA-560 produces a mixture of at least four lipopeptides with seven amino acids incorporated and a fatty acid chain with 14 carbons, which makes this molecule similar to the biosurfactant of Bacillus pumilus, namely, pumilacidin. This is the first report on the biosurfactant production by B. safensis, encompassing the investigation of the metabolic pathway and chemical characterization of the biosurfactant molecule. PMID:25586584

  20. Chemical actions of ionizing radiation on oligopeptide derivatives of glycine in the neutral (Zwitterion) and basic forms

    SciTech Connect

    Garrison, W.M.; Sokol, H.A.

    1980-01-01

    Effects of protonation of the terminal NH/sub 2/ group on the relative yields of reductive deamination and deamidation by e/sup -/ in the ..gamma..-radiolysis of di, tri and tetra glycine in the solid state are described. The experimental data provide direct chemical evidence of specific sites of addition of e/sup -/ to c = o bonds along the peptide chain.

  1. A new cytotoxic prenylated dihydrobenzofuran derivative and other chemical constituents from the rhizomes of Atractylodes lancea DC.

    PubMed

    Duan, Jin-ao; Wang, Liuying; Qian, Shihui; Su, Shulan; Tang, Yuping

    2008-08-01

    A new prenylated dihydrobenzofuran derivative (1), was isolated from the rhizomes of Atractylodes lancea DC (Asteraceae), along with ten known compounds, including atractylenolide II (2), phi-taraxasteryl acetate (3), taraxerol acetate (4), beta-sitosterol (5), stigmasterol (6), beta-eudesmol (7), atractylenolide III (8), atractylenolide IV (9), daucosterol (10), and stigmasterol 3-O-beta-D-glucopyranoside (11). The structure of the new compound (1) was elucidated as trans-2-hydroxyisoxypropyl-3-hydroxy-7-isopentene-2,3-dihydrobenzofuran-5-carboxylic acid by the combination of 1D, 2D NMR analysis and mass spectrometry, and it was the first reported 2,3-dihydrobenzofuran derivative having a carboxyl residue at C-5 and an isopentene moiety at C-7 contemporaneously. In addition, compound 1 exhibited significant cytotoxicity against cancer cell lines HCT-116 and MKN-45. PMID:18787781

  2. Development of a pluripotent stem cell derived neuronal model to identify chemically induced pathway perturbations in relation to neurotoxicity: Effects of CREB pathway inhibition

    SciTech Connect

    Pistollato, Francesca; Louisse, Jochem; Scelfo, Bibiana; Mennecozzi, Milena; Accordi, Benedetta; Basso, Giuseppe; Gaspar, John Antonydas; Zagoura, Dimitra; Barilari, Manuela; Palosaari, Taina; Sachinidis, Agapios; Bremer-Hoffmann, Susanne

    2014-10-15

    According to the advocated paradigm shift in toxicology, acquisition of knowledge on the mechanisms underlying the toxicity of chemicals, such as perturbations of biological pathways, is of primary interest. Pluripotent stem cells (PSCs), such as human embryonic stem cells (hESCs) and human induced pluripotent stem cells (hiPSCs), offer a unique opportunity to derive physiologically relevant human cell types to measure molecular and cellular effects of such pathway modulations. Here we compared the neuronal differentiation propensity of hESCs and hiPSCs with the aim to develop novel hiPSC-based tools for measuring pathway perturbation in relation to molecular and cellular effects in vitro. Among other fundamental pathways, also, the cAMP responsive element binding protein (CREB) pathway was activated in our neuronal models and gave us the opportunity to study time-dependent effects elicited by chemical perturbations of the CREB pathway in relation to cellular effects. We show that the inhibition of the CREB pathway, using 2-naphthol-AS-E-phosphate (KG-501), induced an inhibition of neurite outgrowth and synaptogenesis, as well as a decrease of MAP2{sup +} neuronal cells. These data indicate that a CREB pathway inhibition can be related to molecular and cellular effects that may be relevant for neurotoxicity testing, and, thus, qualify the use of our hiPSC-derived neuronal model for studying chemical-induced neurotoxicity resulting from pathway perturbations. - Highlights: • HESCs derived neuronal cells serve as benchmark for iPSC based neuronal toxicity test development. • Comparisons between hESCs and hiPSCs demonstrated variability of the epigenetic state • CREB pathway modulation have been explored in relation to the neurotoxicant exposure KG-501 • hiPSC might be promising tools to translate theoretical AoPs into toxicological in vitro tests.

  3. A comprehensive description of chemical association effects on second derivative properties of alcohols through a SAFT-VR approach.

    PubMed

    Lafitte, Thomas; Piñeiro, Manuel M; Daridon, Jean-Luc; Bessières, David

    2007-04-01

    A recently derived version of the statistical associating fluid theory (SAFT), denoted as SAFT-VR Mie, which incorporates the Mie potentials within the SAFT-VR framework to model the monomer segment interactions (Lafitte et al. J. Chem. Phys. 2006, 124, 024509), is used for the study of second-order derivative properties and phase equilibria of alcohols and 1-alcohol + n-alkane binary mixtures. For this purpose, a variable repulsive potential is used to induce nonconformal interactions in the reference nonbonded fluid. These features have a significant influence on the chain and association contributions through the contact value of the radial distribution function, and they enhance the SAFT theory performance in the application to associating substances. When dealing with pure alcohols and 1-alcohol + n-alkane binary mixtures, an accurate description of both phase equilibria and second-order derivatives is obtained with a single set of molecular parameters. To explore the predictive ability limit of the model we have particularly focused our attention on secondary derivative properties, which display singularities due to the formation of aggregates. With this approach, we have found that the model is able to reproduce accurately the complex behavior of the isobaric heat capacity of alcohols as, for instance, the maximum versus temperature in the compressed liquid region. Furthermore, in the case of 1-hexanol + n-hexane binary mixtures, the proposed equation is found to capture the association effects on the pressure and temperature dependence of the isobaric thermal expansivity. These two special features, which to our knowledge have never been described by a theoretical model, emphasize both the validity of the changes in the model proposed and the physical meaning of the molecular parameters obtained in this study. PMID:17388508

  4. Shornephine A: Structure, Chemical Stability, and P-Glycoprotein Inhibitory Properties of a Rare Diketomorpholine from an Australian Marine-Derived Aspergillus sp.

    PubMed Central

    2015-01-01

    Chemical analysis of an Australian marine sediment-derived Aspergillus sp. (CMB-M081F) yielded the new diketomorpholine (DKM) shornephine A (1) together with two known and one new diketopiperazine (DKP), 15b-β-hydroxy-5-N-acetyladreemin (2), 5-N-acetyladreemin (3), and 15b-β-methoxy-5-N-acetyladreemin (4), respectively. Structure elucidation of 1–4 was achieved by detailed spectroscopic analysis, supported by chemical degradation and derivatization, and biosynthetic considerations. The DKM (1) underwent a facile (auto) acid-mediated methanolysis to yield seco-shornephine A methyl ester (1a). Our mechanistic explanation of this transformation prompted us to demonstrate that the acid-labile and solvolytically unstable DKM scaffold can be stabilized by N-alkylation. Furthermore, we demonstrate that at 20 μM shornephine A (1) is a noncytotoxic inhibitor of P-glycoprotein-mediated drug efflux in multidrug-resistant human colon cancer cells. PMID:25158286

  5. Comparison between bioconcentration factor (BCF) data provided by industry to the European Chemicals Agency (ECHA) and data derived from QSAR models.

    PubMed

    Petoumenou, Maria I; Pizzo, Fabiola; Cester, Josep; Fernández, Alberto; Benfenati, Emilio

    2015-10-01

    The bioconcentration factor (BCF) is the ratio of the concentration of a chemical in an organism to the concentration in the surrounding environment at steady state. It is a valuable indicator of the bioaccumulation potential of a substance. BCF is an essential environmental property required for regulatory purposes within the Registration, Evaluation, Authorization and restriction of Chemicals (REACH) and Globally Harmonized System (GHS) regulations. In silico models for predicting BCF can facilitate the risk assessment for aquatic toxicology and reduce the cost and number of animals used. The aim of the present study was to examine the correlation of BCF data derived from the dossiers of registered chemicals submitted to the European Chemical Agency (ECHA) with the results of a battery of Quantitative Structure-Activity Relationship (QSAR). After data pruning, statistical analysis was performed using the predictions of the selected models. Results in terms of R(2) had low rating around 0.5 for the pruned dataset. The use of the model applicability domain index (ADI) led to an improvement of the performance for compounds falling within it. The variability of the experimental data and the use of different parameters to define the applicability domain can influence the performance of each model. All available information should be adapted to the requirements of the regulation to obtain a safe decision. PMID:26282223

  6. The Redox Chemistry and Chemical Biology of H2S, Hydropersulfides and Derived Species: Implications to Their Possible Biological Activity and Utility

    PubMed Central

    Ono, Katsuhiko; Akaike, Takaake; Sawa, Tomohiro; Kumagai, Yoshito; Wink, David A.; Tantillo, Dean J.; Hobbs, Adrian J.; Nagy, Peter; Xian, Ming; Lin, Joseph; Fukuto, Jon M.

    2014-01-01

    Hydrogen sulfide (H2S) is an endogenously generated and putative signaling/effector molecule. In spite of its numerous reported functions, the chemistry by which it elicits its functions is not understood. Moreover, recent studies allude to the existence of other sulfur species besides H2S that may play critical physiological roles. Herein, the basic chemical biology of H2S as well as other related or derived species is discussed and reviewed. A particular focus of this review are the per- and poly-sulfides which are likely in equilibrium with free H2S and which may be important biological effectors themselves. PMID:25229186

  7. Chemical insight from density functional modeling of molecular adsorption: Tracking the bonding and diffusion of anthracene derivatives on Cu(111) with molecular orbitals

    NASA Astrophysics Data System (ADS)

    Wyrick, Jonathan; Einstein, T. L.; Bartels, Ludwig

    2015-03-01

    We present a method of analyzing the results of density functional modeling of molecular adsorption in terms of an analogue of molecular orbitals. This approach permits intuitive chemical insight into the adsorption process. Applied to a set of anthracene derivates (anthracene, 9,10-anthraquinone, 9,10-dithioanthracene, and 9,10-diselenonanthracene), we follow the electronic states of the molecules that are involved in the bonding process and correlate them to both the molecular adsorption geometry and the species' diffusive behavior. We additionally provide computational code to easily repeat this analysis on any system.

  8. Chemical insight from density functional modeling of molecular adsorption: Tracking the bonding and diffusion of anthracene derivatives on Cu(111) with molecular orbitals

    SciTech Connect

    Wyrick, Jonathan; Bartels, Ludwig; Einstein, T. L.

    2015-03-14

    We present a method of analyzing the results of density functional modeling of molecular adsorption in terms of an analogue of molecular orbitals. This approach permits intuitive chemical insight into the adsorption process. Applied to a set of anthracene derivates (anthracene, 9,10-anthraquinone, 9,10-dithioanthracene, and 9,10-diselenonanthracene), we follow the electronic states of the molecules that are involved in the bonding process and correlate them to both the molecular adsorption geometry and the species’ diffusive behavior. We additionally provide computational code to easily repeat this analysis on any system.

  9. Polar effects and structural variation in 4-substituted 1-phenylbicyclo[2.2.2]octane derivatives: a quantum chemical study.

    PubMed

    Campanelli, Anna Rita; Domenicano, Aldo; Ramondo, Fabio

    2006-08-24

    The transmission of polar effects through the bicyclo[2.2.2]octane framework has been investigated by ascertaining how the geometry of a phenyl group at a bridgehead position is affected by a variable substituent at the opposite bridgehead position. We have determined the molecular structure of several Ph-C(CH(2)-CH(2))(3)C-X molecules (where X is a charged or dipolar substituent) from HF/6-31G and B3LYP/6-311++G molecular orbital calculations and have progressively replaced each of the three -CH(2)-CH(2)- bridges by a pair of hydrogen atoms. Thus the bicyclo[2.2.2]octane derivatives were changed first into cyclohexane derivatives in the boat conformation, then into n-butane derivatives in the anti-syn-anti conformation, and eventually into assemblies of two molecules, Ph-CH(3) and CH(3)-X, appropriately oriented and kept at a fixed distance. For each variable substituent the deformation of the benzene ring relative to X = H remains substantially the same even when the substituent and the phenyl group are no longer connected by covalent bonds. This provides unequivocal evidence that long-range polar effects in bicyclo[2.2.2]octane derivatives are actually field effects, being transmitted through space rather than through bonds. Varying the substituent X in a series of Ph-C(CH(2)-CH(2))(3)C-X molecules gives rise to geometrical variation (relative to X = H) not only in the benzene ring but also in the bicyclo[2.2.2]octane cage. The two deformations are poorly correlated. The rather small deformation of the benzene ring correlates well with traditional measures of long-range polar effects in bicyclo[2.2.2]octane derivatives, such as sigma(F) or sigma(I) values. The much larger deformation of the bicyclo[2.2.2]octane cage is controlled primarily by the electronegativity of X, similar to deformation of the benzene ring in Ph-X molecules. Thus the field and electronegativity effects of the substituent are well separated and can be studied simultaneously, as they act on different parts of the molecular skeleton. PMID:16913687

  10. Chemical abundances of planetary nebulae from optical recombination lines - II. Abundances derived from collisionally excited lines and optical recombination lines

    NASA Astrophysics Data System (ADS)

    Liu, Y.; Liu, X.-W.; Barlow, M. J.; Luo, S.-G.

    2004-10-01

    In Paper I, we presented spectrophotometric measurements of emission lines from the ultraviolet (UV) to the far-infrared for 12 Galactic planetary nebulae (PNe) and derived nebular thermal and density structures using a variety of plasma diagnostics. The measurements and plasma diagnostic results are used in the current paper to determine elemental abundances in these nebulae. Abundance analyses are carried out using both strong collisionally excited lines (CELs) and weak optical recombination lines (ORLs) from heavy element ions. Assuming electron temperatures and densities derived from HI recombination spectra (line and continuum), we are able to determine the ORL C abundance relative to hydrogen for all the PNe in our sample, N and O abundances for 11 of them and Ne abundances for nine of them. In all cases, ORL abundances are found to be systematically higher than the corresponding values deduced from CELs. In NGC 40, the discrepancy between the abundances derived from the two types of emission line reaches a factor of 17 for oxygen. For the other 10 PNe, the discrepancies for oxygen vary from 1.6 to 3.1. In general, collisionally excited infrared fine-structure lines, which have excitation energies less than 103 K and consequently emissivities that are insensitive to electron temperature and temperature fluctuations, yield ionic abundances comparable to those derived from optical/UV CELs. For a given nebula, the discrepancies between the ORL and CEL abundances are of similar magnitude for different elements. In other words, relative abundance ratios such as C/O, N/O and Ne/O deduced from the traditional method based on strong CELs are comparable to those yielded by ORLs, for a wide range of ORL to CEL oxygen abundance ratios, varying from near unity to over a factor of 20. We have also determined ORL abundances relative to hydrogen for the third-row element magnesium for 11 nebulae in our sample. In strong contrast to the cases for second-row elements, Mg abundances derived from the MgII 3d-4f λ4481 ORL are nearly constant for all the PNe analysed so far and agree within the uncertainties with the solar photospheric value. In accordance with results from previous studies, the ORL to CEL abundance ratio is correlated with the difference between the electron temperatures derived from the [OIII] forbidden-line ratio, on the one hand, and from the hydrogen recombination Balmer discontinuity, on the other. We find that the discrepancy between the ORL and CEL abundances is correlated with nebular absolute diameter, surface brightness, the electron density derived from [SII] CELs, and excitation class. The results confirm that the dichotomy of temperatures and heavy elemental abundances determined from the two types of emission line, which has been widely observed in PNe, is a strong function of nebular evolution, as first pointed out by Garnett and Dinerstein. Our analyses show that temperature fluctuations and/or density inhomogeneities are incapable of explaining the large discrepancies between the heavy elemental abundances and electron temperatures determined from the two types of emission line. Our analyses support the bi-abundance model of Liu et al., who have proposed that PNe contain another previously unseen component of ionized gas which, highly enriched in heavy elements, has an electron temperature of <~103 K and emits strongly in recombination lines but not in CELs. Our determinations of low average emission temperatures from the observed line intensity ratios of HeI and OII ORLs lend further support to this scenario.

  11. Biogenic Synthesis, Purification, and Chemical Characterization of Anti-inflammatory Resolvins Derived from Docosapentaenoic Acid (DPAn-6)

    PubMed Central

    Dangi, Bindi; Obeng, Marcus; Nauroth, Julie M.; Teymourlouei, Mah; Needham, Micah; Raman, Krishna; Arterburn, Linda M.

    2009-01-01

    Enzymatically oxygenated derivatives of the ω-3 fatty acids cis-4,7,10,13,16,19-docosahexaenoic acid (DHA) and cis-5,8,11,14,17-eicosapentaenoic acid, known as resolvins, have potent inflammation resolution activity (Serhan, C. N., Clish, C. B., Brannon, J., Colgan, S. P., Chiang, N., and Gronert, K. (2000) J. Exp. Med. 192, 1197–1204; Hong, S., Gronert, K., Devchand, P. R., Moussignac, R., and Serhan, C. N. (2003) J. Biol. Chem. 278, 14677–14687). Our objective was to determine whether similar derivatives are enzymatically synthesized from other C-22 fatty acids and whether these molecules possess inflammation resolution properties. The reaction of DHA, DPAn-3, and DPAn-6 with 5-, 12-, and 15-lipoxygenases produced oxylipins, which were identified and characterized by liquid chromatography coupled with tandem mass-spectrometry. DPAn-6 and DPAn-3 proved to be good substrates for 15-lipoxygenase. 15-Lipoxygenase proved to be the most efficient enzyme of the three tested for conversion of long chain polyunsaturated fatty acids to corresponding oxylipins. Since DPAn-6 is a major component of Martek DHA-S™ oil, we focused our attention on reaction products obtained from the DPAn-6 and 15-lipoxygenase reaction. (17S)-hydroxy-DPAn-6 and (10,17S)-dihydroxy-DPAn-6 were the main products of this reaction. These compounds were purified by preparatory high performance liquid chromatography techniques and further characterized by NMR, UV spectrophotometry, and tandem mass spectrometry. We tested both compounds in two animal models of acute inflammation and demonstrated that both compounds are potent anti-inflammatory agents that are active on local intravenous as well as oral administration. These oxygenated DPAn-6 compounds can thus be categorized as a new class of DPAn-6-derived resolvins. PMID:19324874

  12. Human Induced Pluripotent Stem Cell Derived Neuronal Cells Cultured on Chemically-Defined Hydrogels for Sensitive In Vitro Detection of Botulinum Neurotoxin.

    PubMed

    Pellett, Sabine; Schwartz, Michael P; Tepp, William H; Josephson, Richard; Scherf, Jacob M; Pier, Christina L; Thomson, James A; Murphy, William L; Johnson, Eric A

    2015-01-01

    Botulinum neurotoxin (BoNT) detection provides a useful model for validating cell-based neurotoxicity screening approaches, as sensitivity is dependent on functionally competent neurons and clear quantitative endpoints are available for correlating results to approved animal testing protocols. Here, human induced pluripotent stem cell (iPSC)-derived neuronal cells were cultured on chemically-defined poly(ethylene glycol) (PEG) hydrogels formed by "thiol-ene" photopolymerization and tested as a cell-based neurotoxicity assay by determining sensitivity to active BoNT/A1. BoNT/A1 sensitivity was comparable to the approved in vivo mouse bioassay for human iPSC-derived neurons and neural stem cells (iPSC-NSCs) cultured on PEG hydrogels or treated tissue culture polystyrene (TCP) surfaces. However, maximum sensitivity for BoNT detection was achieved two weeks earlier for iPSC-NSCs that were differentiated and matured on PEG hydrogels compared to TCP. Therefore, chemically-defined synthetic hydrogels offer benefits over standard platforms when optimizing culture conditions for cell-based screening and achieve sensitivities comparable to an approved animal testing protocol. PMID:26411797

  13. Comparative molecular field analysis and comparative molecular similarity index analysis studies on 1H NMR chemical shift of NH group of diaryl triazene derivatives.

    PubMed

    Rofouie, M K; Salahinejad, M; Ghasemi, J B; Aghaei, A

    2013-05-01

    Comparative molecular field analysis (CoMFA), comparative molecular field analysis region focusing (CoMFA-RF) for optimizing the region for the final partial least square analysis, and comparative molecular similarity indices analysis (CoMSIA) methods were employed to develop three-dimensional quantitative structure-activity relationship (3D-QSAR) models of (1)H NMR chemical shift of NH proton of diaryl triazene derivatives. The best orientation was searched by all-orientation search (AOS) strategy to minimize the effect of the initial orientation of the structures. The predictive abilities of CoMFA-RF and CoMSIA models were determined using a test set of ten compounds affording predictive correlation coefficients of 0.721 and 0.754, respectively, indicating good predictive power. For further model validation, cross validation (leave one out), progressive scrambling, and bootstrapping were also applied. The accuracy and speed of obtained 3D-QSAR models for the prediction of (1)H NMR chemical shifts of NH group of diaryl triazene derivatives were greater compared to some computational well-known procedures. PMID:23456682

  14. Human Induced Pluripotent Stem Cell Derived Neuronal Cells Cultured on Chemically-Defined Hydrogels for Sensitive In Vitro Detection of Botulinum Neurotoxin

    PubMed Central

    Pellett, Sabine; Schwartz, Michael P.; Tepp, William H.; Josephson, Richard; Scherf, Jacob M.; Pier, Christina L.; Thomson, James A.; Murphy, William L.; Johnson, Eric A.

    2015-01-01

    Botulinum neurotoxin (BoNT) detection provides a useful model for validating cell-based neurotoxicity screening approaches, as sensitivity is dependent on functionally competent neurons and clear quantitative endpoints are available for correlating results to approved animal testing protocols. Here, human induced pluripotent stem cell (iPSC)-derived neuronal cells were cultured on chemically-defined poly(ethylene glycol) (PEG) hydrogels formed by “thiol-ene” photopolymerization and tested as a cell-based neurotoxicity assay by determining sensitivity to active BoNT/A1. BoNT/A1 sensitivity was comparable to the approved in vivo mouse bioassay for human iPSC-derived neurons and neural stem cells (iPSC-NSCs) cultured on PEG hydrogels or treated tissue culture polystyrene (TCP) surfaces. However, maximum sensitivity for BoNT detection was achieved two weeks earlier for iPSC-NSCs that were differentiated and matured on PEG hydrogels compared to TCP. Therefore, chemically-defined synthetic hydrogels offer benefits over standard platforms when optimizing culture conditions for cell-based screening and achieve sensitivities comparable to an approved animal testing protocol. PMID:26411797

  15. Structure and physico-chemical properties of hexadentate Schiff base zinc complexes derived from salicylaldehydes and triethylenetetramine*1

    NASA Astrophysics Data System (ADS)

    Chantarasiri, Nuanphun; Ruangpornvisuti, Vithaya; Muangsin, Nongnuj; Detsen, Hussadee; Mananunsap, Thussanee; Batiya, Chureephon; Chaichit, Narongsak

    2004-09-01

    Two hexadentate Schiff base zinc complexes, ZnSal 2trien and ZnVan 2trien, where Sal=salicylaldehyde, Van= o-vanillin, and trien=triethylenetetramine, have been synthesized by the reaction between salicylaldehydes, triethylenetetramine and zinc acetate. The structure of ZnSal 2trien and ZnVan 2trien were determined by single crystal X-ray crystallography. It was found that both ZnSal 2trien and ZnVan 2trien have a bent-shaped structure. Properties of the complexes were examined using differential scanning calorimetry, polarized optical microscopy and small angle X-ray scattering. Protonation constants of the ligands Sal 2trien and Van 2trien and stability constants of their zinc complexes were determined by potentiometric titration. Binding energies of ZnSal 2trien and ZnVan 2trien complexes were obtained by quantum chemical calculations.

  16. The effects of activation temperature on physico-chemical characteristics of activated carbons derived from biomass wastes

    NASA Astrophysics Data System (ADS)

    Sutrisno, Bachrun; Hidayat, Arif

    2015-12-01

    This research focused on investigating in the effect of activation temperature on the physico-chemical properties of palm empty fruit bunch (PEFB) based activated carbon prepared by physical activation with carbon dioxide. The activation temperature was studied in the range of 400-800°C by keeping the activation temperature at 800°C for 120 min. It was found that the porous properties of activated carbon decreased with an increase in carbonization temperature. The activated carbons prepared at the highest activation temperature at 800°C and activation time of 120 min gave the activated carbon with the highest of BET surface area and pore volume of 938 m2/g and 0.4502 cm3/g, respectively

  17. Coumarins from the Herb Cnidium monnieri and Chemically Modified Derivatives as Antifoulants against Balanus albicostatus and Bugula neritina Larvae

    PubMed Central

    Wang, Zhan-Chang; Feng, Dan-Qing; Ke, Cai-Huan

    2013-01-01

    In the search for new environmental friendly antifouling (AF) agents, four coumarins were isolated from the herbal plant Cnidium monnieri, known as osthole (1), imperatorin (2), isopimpinellin (3) and auraptenol (4). Furthermore, five coumarin derivatives, namely 8-epoxypentylcoumarin (5), meranzin hydrate (6), 2′-deoxymetranzin hydrate (7), 8-methylbutenalcoumarin (8), and micromarin-F (9) were synthesized from osthole. Compounds 1, 2, 4, 7 showed high inhibitory activities against larval settlement of Balanus albicostatus with EC50 values of 4.64, 3.39, 3.38, 4.67 μg mL−1. Compound 8 could significantly inhibit larval settlement of Bugula neritina with an EC50 value of 3.87 μg mL−1. The impact of functional groups on anti-larval settlement activities suggested that the groups on C-5′ and C-2′/C-3′ of isoamylene chian could affect the AF activities. PMID:23303279

  18. Chemical Conjugation of Evans Blue Derivative: A Strategy to Develop Long-Acting Therapeutics through Albumin Binding

    PubMed Central

    Chen, Haojun; Wang, Guohao; Lang, Lixin; Jacobson, Orit; Kiesewetter, Dale O.; Liu, Yi; Ma, Ying; Zhang, Xianzhong; Wu, Hua; Zhu, Lei; Niu, Gang; Chen, Xiaoyuan

    2016-01-01

    The efficacy of therapeutic drugs is highly dependent on their optimal in vivo pharmacokinetics. Albumin conjugation is considered to be one of the most effective means of protracting the short lifespan of peptides and proteins. In this study, we proposed a novel platform for developing long lasting therapeutics by conjugating a small molecular albumin binding moiety, truncated Evans blue, to either peptides or proteins. Using the anti-diabetic peptide drug Exendin-4 as a model peptide, we synthesized a new long-acting Exendin-4 derivative (denoted as Abextide). Through complexation with albumin in situ, the biological half-life of Abextide was significantly extended. The hypoglycemic effect of Abextide was also improved remarkably over Exendin-4. Thus, Abextide has considerable potential to treat type 2 diabetes. This strategy as a general technology platform can be applied to other small molecules and biologics for the development of long-acting therapeutic drugs. PMID:26877782

  19. Chemical modification of silica gel with synthesized new Schiff base derivatives and sorption studies of cobalt (II) and nickel (II)

    NASA Astrophysics Data System (ADS)

    Kursunlu, Ahmed Nuri; Guler, Ersin; Dumrul, Hakan; Kocyigit, Ozcan; Gubbuk, Ilkay Hilal

    2009-08-01

    In this study, three Schiff base ligands and their complexes were synthesized and characterized by infrared spectroscopy (IR), thermogravimetric analyses (TGA), nuclear magnetic resonance (NMR), elemental analysis and magnetic susceptibility apparatuses. Silica gel was respectively modified with Schiff base derivatives, (E)-2-[(2-chloroethylimino)methyl]phenol, (E)-4-[(2-chloroethylimino)methyl]phenol and N, N'-[1,4-phenilendi(E)methylidene]bis(2-chloroethanamine), after silanization of silica gel by (3-aminopropyl)trimethoxysilane (APTS) by using a suitable method. Characterization of the surface modification was also performed with IR, TGA and elemental analysis. The immobilized surfaces were used for Co(II) and Ni(II) sorption from aqueous solutions and values of sorption were detected by atomic absorption spectrometer (AAS).

  20. Coumarins from the Herb Cnidium monnieri and chemically modified derivatives as antifoulants against Balanus albicostatus and Bugula neritina larvae.

    PubMed

    Wang, Zhan-Chang; Feng, Dan-Qing; Ke, Cai-Huan

    2013-01-01

    In the search for new environmental friendly antifouling (AF) agents, four coumarins were isolated from the herbal plant Cnidium monnieri, known as osthole (1), imperatorin (2), isopimpinellin (3) and auraptenol (4). Furthermore, five coumarin derivatives, namely 8-epoxypentylcoumarin (5), meranzin hydrate (6), 2'-deoxymetranzin hydrate (7), 8-methylbutenalcoumarin (8), and micromarin-F (9) were synthesized from osthole. Compounds 1, 2, 4, 7 showed high inhibitory activities against larval settlement of Balanus albicostatus with EC(50) values of 4.64, 3.39, 3.38, 4.67 μg mL-1. Compound 8 could significantly inhibit larval settlement of Bugula neritina with an EC(50) value of 3.87 μg mL-1. The impact of functional groups on anti-larval settlement activities suggested that the groups on C-5' and C-2'/C-3' of isoamylene chian could affect the AF activities. PMID:23303279

  1. Optical Fiber Chemical Sensor with Sol-Gel Derived Refractive Material as Transducer for High Temperature Gas Sensing in Clean Coal Technology

    SciTech Connect

    Shiquan Tao

    2006-12-31

    The chemistry of sol-gel derived silica and refractive metal oxide has been systematically studied. Sol-gel processes have been developed for preparing porous silica and semiconductor metal oxide materials. Micelle/reversed micelle techniques have been developed for preparing nanometer sized semiconductor metal oxides and noble metal particles. Techniques for doping metal ions, metal oxides and nanosized metal particles into porous sol-gel material have also been developed. Optical properties of sol-gel derived materials in ambient and high temperature gases have been studied by using fiber optic spectroscopic techniques, such as fiber optic ultraviolet/visible absorption spectrometry, fiber optic near infrared absorption spectrometry and fiber optic fluorescence spectrometry. Fiber optic spectrometric techniques have been developed for investigating the optical properties of these sol-gel derived materials prepared as porous optical fibers or as coatings on the surface of silica optical fibers. Optical and electron microscopic techniques have been used to observe the microstructure, such as pore size, pore shape, sensing agent distribution, of sol-gel derived material, as well as the size and morphology of nanometer metal particle doped in sol-gel derived porous silica, the nature of coating of sol-gel derived materials on silica optical fiber surface. In addition, the chemical reactions of metal ion, nanostructured semiconductor metal oxides and nanometer sized metal particles with gas components at room temperature and high temperatures have also been investigated with fiber optic spectrometric methods. Three classes of fiber optic sensors have been developed based on the thorough investigation of sol-gel chemistry and sol-gel derived materials. The first group of fiber optic sensors uses porous silica optical fibers doped with metal ions or metal oxide as transducers for sensing trace NH{sub 3} and H{sub 2}S in high temperature gas samples. The second group of fiber optic sensors uses sol-gel derived porous silica materials doped with nanometer particles of noble metals in the form of fiber or coating for sensing trace H{sub 2}, NH{sub 3} and HCl in gas samples at for applications ambient temperature. The third classes of fiber optic sensors use sol-gel derived semiconductor metal oxide coating on the surface of silica optical fiber as transducers for selectively sensing H{sub 2}, CH{sub 4} and CO at high temperature. In addition, optical fiber temperature sensors use the fluorescence signal of rare-earth metal ions doped porous silica optical fiber or the optical absorption signal of thermochromic metal oxide materials coated on the surface of silica optical fibers have also been developed for monitoring gas temperature of corrosive gas. Based on the results obtained from this project, the principle of fiber optic sensor techniques for monitoring matrix gas components as well as trace components of coal gasification derived syngas has been established. Prototype sensors for sensing trace ammonia and hydrogen sulfide in gasification derived syngas have been built up in our laboratory and have been tested using gas samples with matrix gas composition similar to that of gasification derived fuel gas. Test results illustrated the feasibility of these sensors for applications in IGCC processes.

  2. Derived no-effect levels (DNELs) under the European chemicals regulation REACH--an analysis of long-term inhalation worker-DNELs presented by industry.

    PubMed

    Schenk, Linda; Deng, Uriell; Johanson, Gunnar

    2015-05-01

    The European REACH regulation places responsibility for providing safety information, including derived no-effect levels (DNELs), on chemicals and chemical products on 'industry', i.e. manufacturers and importers. We compared long-term inhalation worker-DNELs (wDNELs) presented by industry with the corresponding Swedish occupational exposure limits (OELs), and for a subset, with wDNELs derived by us. Our wDNELs were derived using toxicological evaluations published by the Swedish Criteria Group and our interpretation of the REACH Guidance. On average, industry's wDNELs were the same as the Swedish OELs (median of wDNEL-OEL ratios: 0.98, n = 235). However, the variation was huge, the extremes being up to 450 times higher, and up to 230 times lower than the corresponding OEL. Nearly one-fifth of the wDNELs were ≥2 times higher and one-third ≥2 times lower than the OEL. No time trend was seen in the wDNEL/OEL ratios, suggesting that older OELs were not systematically higher than the more recent ones. Industry's wDNELs varied widely and were generally higher (median 4.2 times, up to 435 times higher, down to 13 times lower, n = 23) also compared to our wDNELs. Only five industry wDNELs were equal to or lower than ours. The choices of key studies, dose descriptors, and assessment factors all seemed to contribute to the discrepancies. We conclude that although the REACH guidance is detailed, many choices that will influence the wDNEL lack firm instructions. A major problem is that little advice is given on when and how to depart from default assessment factors. PMID:25471229

  3. Quantum-chemical calculations of the electronic structure of 2-amino-1,3-dicyano-5,6,7,8-tetrahydronaphthalene derivatives.

    PubMed

    Jzefowicz, M; Bajorek, A; Pietrzak, M; Heldt, J R

    2013-09-01

    The UV-Visible absorption spectra of six, newly synthesized donor-substituted 2-amino-1,3-dicyano-5,6,7,8-tetrahydronaphthalene have been measured in methylcyclohexane (MCH) and assigned with the help of quantum-chemical calculations. Our calculations have been performed to assess information regarding the electronic state energy values, corresponding oscillator strengths, x-, y-, z-components of the transition dipole moments and molecular orbitals involved in the main electronic transitions of the studied compounds. Additionally, the experimental absorption transition dipole moments were calculated, on the basis of spectroscopic data, and compared with results of our quantum-chemical calculations. On the basis of the experimental results and quantum-chemical calculations, it was shown that the long-wavelength absorption band involves an overlap of three electronic transitions of different character. For all studied donor-acceptor (D-A) compounds in vapour-phase, the long-wavelength transition (S0?S1) does not possess charge transfer character, whereas the S0?S2 transition possesses electron transfer character e.g., ?-electrons of the acceptor moiety are moved to the donor part. Moreover, it is found that the electronic structure of the studied biphenyl derivatives can be approximately described within composite-model of decoupled moieties: donor and acceptor. PMID:23719413

  4. Improved activity and stability of alkaline phosphatases from psychrophilic and mesophilic organisms by chemically modifying aliphatic or amino groups using tetracarboxy-benzophenone derivatives.

    PubMed

    Siddiqui, K S; Poljak, A; Cavicchioli, R

    2004-07-01

    The activity-stability-structure relationship of the cold-active alkaline phosphatase from Red Arctic shrimp, Pandalus borealis (SAP) was studied by chemically modifying aliphatic (C-H) or amino (NH2) groups using benzophenone tetracarboxylic derivatives in either a light (UV-A) or dark reaction. The response of the cold-adapted enzyme was compared to a similarly modified calf alkaline phosphatase (CAP). MALDI-TOF-MS was used to determine the extent and nature of the modifications in both SAP and CAP. On average 2 to 4 amino acid residues were linked to a BP-modifier, with up to 18 to 21 amino acids modified in a smaller portion of the material. The effect of the modifications on kinetic and thermodynamic properties varied with the enzyme and type of modification. The aliphatic-group modified SAP demonstrated typical characteristics of a mesophilic enzyme, consistent with an activity-stability trade-off where gain in thermostability was attained at the expense of decreased activity. In contrast, the activity of the amino-group modified SAP attained an even more psychrophilic character with respect to its kinetic (increase in kcat and Km) and thermodynamic (reduction in deltaH#) properties. Interestingly, the amino-group modified SAP also acquired higher thermostability, thus demonstrating that both activity and stability can be simultaneously enhanced using chemical modification. The study demonstrates the applicability of benzophenone chemical modification for improving the thermal properties of enzymes from psychrophiles and mesophiles. PMID:15559981

  5. Membranes as programmable matter: modulating physical-chemical behavior in lipid ensembles derived from archaea and eukaryotes

    NASA Astrophysics Data System (ADS)

    Gilmore, Sean Fitzpatrick

    Lipid membranes are of general interest to the scientific community due to their roles as cellular membranes, and because of their interesting material properties, such as tendencies to self-assemble into two- and three-dimensional structures. Further, there is interest in using lipid membranes as a self-assembling template or substrate for other materials, such as membrane proteins. The work presented here explores the physical-chemical interactions in and around artificial lipid membranes. In the first two chapters, lipid membranes are investigated as a form of programmable matter that responds to environmental changes. These responses manifest as two- and three-dimensional reorganization. In the subsequent chapters, the lipids of an extremophilic archaeon are examined in synthetic configurations to 1) identify how ensembles of lipids originating from organisms of different domains on the tree of life may behave in similar ways, and 2) to examine how the lipids of a desiccation-tolerant organism may be used to create robust lipid (bilayer) membranes that do not rely on liquid water to retain their structure. These collected findings expand how living membranes may be modulated or reorganized in vivo, and also suggest new ways to create programmable lipid-based materials.

  6. Influence of Stoichiometry on the Optical and Electrical Properties of Chemical Vapor Deposition Derived MoS2

    PubMed Central

    2015-01-01

    Ultrathin transition metal dichalcogenides (TMDCs) of Mo and W show great potential for digital electronics and optoelectronic applications. Whereas early studies were limited to mechanically exfoliated flakes, the large-area synthesis of 2D TMDCs has now been realized by chemical vapor deposition (CVD) based on a sulfurization reaction. The optoelectronic properties of CVD grown monolayer MoS2 have been intensively investigated, but the influence of stoichiometry on the electrical and optical properties has been largely overlooked. Here we systematically vary the stoichiometry of monolayer MoS2 during CVD via controlled sulfurization and investigate the associated changes in photoluminescence and electrical properties. X-ray photoelectron spectroscopy is employed to measure relative variations in stoichiometry and the persistence of MoOx species. As MoS2−δ is reduced (increasing δ), the field-effect mobility of monolayer transistors increases while the photoluminescence yield becomes nonuniform. Devices fabricated from monolayers with the lowest sulfur content have negligible hysteresis and a threshold voltage of ∼0 V. We conclude that the electrical and optical properties of monolayer MoS2 crystals can be tuned via stoichiometry engineering to meet the requirements of various applications. PMID:25223821

  7. Process related effects on the chemical and toxicologic characteristics of coal derived fuels. [Changes over 25 day run

    SciTech Connect

    Wright, C.W.; Chess, E.K.; Bean, R.M.; Mahlum, D.D.; Stewart, D.L.; Wilson, B.W.

    1986-04-01

    As a component of an ongoing program to assess the potential health effects of coal conversion materials, the authors have recently completed chemical and toxicologic studies of a sample set collected on selected days of a 25-day demonstration run of a catalytic two stage direct coal liquefaction (CTSL) process. There was an increase in heteroatomic, nitrogen containing polycyclic aromatic compounds (NPAC) and hydroxy-substituted PAC, compounds as the operation time of the pilot plant increased. The proportion of material which boiled above 975/sup 0/F also increased in the solids-free portion of the recycle slurry oil as pilot plant operation time increased. As anticipated from the increase in NPAC concentration during the run, the microbial mutagenic activity of selected process materials also increased as a function of run time. Likewise, the tumorigenicity of the materials produced later in the demonstration run was higher than that of those produced initially. These results support the view that catalyst deactivation during the course of the run gives rise not only to lower coal conversion, but also to increased toxicologic activity.

  8. Influence of stoichiometry on the optical and electrical properties of chemical vapor deposition derived MoS2.

    PubMed

    Kim, In Soo; Sangwan, Vinod K; Jariwala, Deep; Wood, Joshua D; Park, Spencer; Chen, Kan-Sheng; Shi, Fengyuan; Ruiz-Zepeda, Francisco; Ponce, Arturo; Jose-Yacaman, Miguel; Dravid, Vinayak P; Marks, Tobin J; Hersam, Mark C; Lauhon, Lincoln J

    2014-10-28

    Ultrathin transition metal dichalcogenides (TMDCs) of Mo and W show great potential for digital electronics and optoelectronic applications. Whereas early studies were limited to mechanically exfoliated flakes, the large-area synthesis of 2D TMDCs has now been realized by chemical vapor deposition (CVD) based on a sulfurization reaction. The optoelectronic properties of CVD grown monolayer MoS2 have been intensively investigated, but the influence of stoichiometry on the electrical and optical properties has been largely overlooked. Here we systematically vary the stoichiometry of monolayer MoS2 during CVD via controlled sulfurization and investigate the associated changes in photoluminescence and electrical properties. X-ray photoelectron spectroscopy is employed to measure relative variations in stoichiometry and the persistence of MoOx species. As MoS2-? is reduced (increasing ?), the field-effect mobility of monolayer transistors increases while the photoluminescence yield becomes nonuniform. Devices fabricated from monolayers with the lowest sulfur content have negligible hysteresis and a threshold voltage of ? 0 V. We conclude that the electrical and optical properties of monolayer MoS2 crystals can be tuned via stoichiometry engineering to meet the requirements of various applications. PMID:25223821

  9. Chemical characteristics and enhanced hepatoprotective activities of Maillard reaction products derived from milk protein-sugar system.

    PubMed

    Oh, Nam Su; Young Lee, Ji; Lee, Hyun Ah; Joung, Jae Yeon; Shin, Yong Kook; Kim, Sae Hun; Kim, Younghoon; Lee, Kwang Won

    2016-02-01

    The objective of this study was to investigate the characteristics, antioxidative properties, and hepatoprotective effects of Maillard reaction products (MRP) from milk protein reacted with sugars. The MRP were obtained from milk protein, whey protein concentrates and sodium caseinate, using 2 types of sugars, lactose and glucose, by heating the mixture at 55°C for 7d in a sodium phosphate buffer (pH 7.4). Changes in the chemical modification of the milk protein were monitored by measuring the protein-bound carbonyls and PAGE protein profiles. The results showed that the amount of protein-bound carbonyls increased after Maillard reaction (MR). In addition, sodium dodecyl sulfate-PAGE analysis indicated a formation of high-molecular weight complexes through MR. The modification sites induced by MR of milk protein were monitored by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry analysis of tryptic-digested gel spots of MRP. As a result, modification and their localization in AA sequence of MRP was identified. Also, the MRP showed higher antioxidant activities than the intact milk protein, and they reduced intracellular reactive oxygen species production and inhibited the depletion of the reduced glutathione concentrations in the HepG2 cells. In particular, glucose-sodium caseinate MRP showed the highest biological activities among all MRP. Therefore, these results suggest that the MRP from milk protein reacting with sugars possess effective antioxidant activity and have a protective ability against oxidative damage. PMID:26627852

  10. Morphology induced photo-degradation study of low temperature, chemically derived ZnO/SnO2 heterostructure

    NASA Astrophysics Data System (ADS)

    Pal, Shreyasi; Maiti, Soumen; Chattopadhyay, Kalyan Kumar

    2016-05-01

    Rational construction of heterostructure is a key pathway to pursue highly active photocatalysts that also offers prospects to explore the relationship between structural aspect and photocatalytic efficiency. Here, we adopted a two-step wet chemical protocol for decoration of ZnO nanowires with SnO2 nanoclusters. ZnO nanowires were prepared by one pot ambient conditioned synthesis from commercial zinc powder. In sequence, synthesized ZnO nanowires were engineered with varying quantity SnO2 nanoclusters via low temperature hydrothermal method. Environmental remediation through catalytic activity of the samples was inspected taking two dyes having different ionic character (Methyl Orange and Rhodamine B) under UV irradiation where the optimized hybrid displayed better performance than mono component oxides. Enhancement in catalytic performance could be enlightened by the heterostructure formation at the ZnO/SnO2 interface which in turns prolonged photogenerated carrier separation and extend the photo response range. Furthermore, the photocatalysis performance by heterostructure could be recycled for several times without noticeable decrease in their catalytic activity.

  11. Effects of lithium doping on microstructure, electrical properties, and chemical bonds of sol-gel derived NKN thin films

    NASA Astrophysics Data System (ADS)

    Lin, Chun-Cheng; Chen, Chan-Ching; Weng, Chung-Ming; Chu, Sheng-Yuan; Hong, Cheng-Shong; Tsai, Cheng-Che

    2015-02-01

    Highly (100/110) oriented lead-free Lix(Na0.5K0.5)1-xNbO3 (LNKN, x = 0, 0.02, 0.04, and 0.06) thin films are fabricated on Pt/Ti/SiO2/Si substrates via a sol-gel processing method. The lithium (Li) dopants modify the microstructure and chemical bonds of the LNKN films, and therefore improve their electrical properties. The optimal values of the remnant polarization (Pr = 14.3 μC/cm2), piezoelectric coefficient (d33 = 48.1 pm/V), and leakage current (<10-5 A/cm2) are obtained for a lithium addition of x = 0.04 (i.e., 4 at. %). The observation results suggest that the superior electrical properties are the result of an improved crystallization, a larger grain size, and a smoother surface morphology. It is shown that the ion transport mechanism is dominated by an Ohmic behavior under low electric fields and the Poole-Frenkel emission effect under high electric fields.

  12. UV-vis spectroscopy and semiempirical quantum chemical studies on methyl derivatives of annulated analogues of azafluoranthene and azulene dyes

    NASA Astrophysics Data System (ADS)

    Danel, K. S.; G?siorski, P.; Matusiewicz, M.; Ca?us, S.; Uchacz, T.; Kityk, A. V.

    2010-09-01

    Paper reports the measured optical absorption and fluorescence spectra of 4-(2-chlorophenyl)-7-methyl-1,3-diphenyl-1 H-pyrazolo[3,4-b]quinoline (MCPDPPQ), as well as 6-methyl-1,3-diphenyl-3 H-indeno[1,2,3- de]pyrazolo[3,4- b]quinoline (MDPIPQ) and 9-methyl-6-phenyl-6 H-5,6,7-triazadibenzo[ f,h]naphtho[3,2,1- cd]azulene (MPTNA) representing cyclized five- or seven-membered regioisomeric products of MCPDPPQ, respectively. The spectra has been recorded in solvents of different polarity and compared with the results of quantum chemical calculations performed by means of the semiempirical method PM3 in combination with molecular dynamics (MD) simulations. Cyclization of MCPDPPQ into MDPIPQ or MPTNA is accompanied by a significant red shift of the first optical absorption and fluorescence bands. While the solvent polarity rises all the dyes exhibit the blue shift of the first absorption band and the red shift of the fluorescence band. These trends have been reproduced within the semiempirical calculations in combination with the Lippert-Mataga dielectric polarization model and explained by specific orientations of the dipole moments in the ground and excited states. All dyes may be considered as candidates for the luminescent or electroluminescent applications. Depending on solvent polarity they emit light in the green-yellow range of the visible spectra.

  13. Optical absorption measurements and quantum-chemical simulations of optical properties of novel fluoro derivatives of pyrazoloquinoline

    NASA Astrophysics Data System (ADS)

    Brik, M. G.; Kuznik, W.; Gondek, E.; Kityk, I. V.; Uchacz, T.; Szlachcic, P.; Jarosz, B.; Plucinski, K. J.

    2010-05-01

    The results of experimental research and quantum-chemical simulations of the absorption spectra of 1-(4-fluorophenyl)-3,4-diphenyl, 3-(4-fluorophenyl)-1,4-diphenyl, and 4-(4-fluorophenyl)-1,3-diphenyl-pyrazolo[3,4- b] quinoline are presented. Although the fluorine atom is located on different phenyl rings in these molecules, the absorption spectra do not differ significantly. Semi-empirical AM1, PM3 and RM1 methods, as well as ab initio ADF code-based calculations were used to optimize geometry, calculate the infrared and visible spectra of the afore mentioned compounds and analyze the molecular orbitals schemes. The results of calculations are in good agreement with the experimental data. It was also demonstrated that the positions of the fluorescence maxima depend significantly on the solvent (contrary to the absorption spectra), in which the molecules are embedded, which allows for manipulating with fluorescence properties of the synthesized molecules by changing the solvent.

  14. Isolation and chemical identification of lipid derivatives from avocado (Persea americana) pulp with antiplatelet and antithrombotic activities.

    PubMed

    Rodriguez-Sanchez, Dariana Graciela; Flores-García, Mirthala; Silva-Platas, Christian; Rizzo, Sheryl; Torre-Amione, Guillermo; De la Peña-Diaz, Aurora; Hernández-Brenes, Carmen; García-Rivas, Gerardo

    2015-01-01

    Platelets play a pivotal role in physiological hemostasis. However, in coronary arteries damaged by atherosclerosis, enhanced platelet aggregation, with subsequent thrombus formation, is a precipitating factor in acute ischemic events. Avocado pulp (Persea americana) is a good source of bioactive compounds, and its inclusion in the diet as a source of fatty acid has been related to reduced platelet aggregability. Nevertheless, constituents of avocado pulp with antiplatelet activity remain unknown. The present study aims to characterize the chemical nature of avocado constituents with inhibitory effects on platelet aggregation. Centrifugal partition chromatography (CPC) was used as a fractionation and purification tool, guided by an in vitro adenosine diphosphate (ADP), arachidonic acid or collagen-platelet aggregation assay. Antiplatelet activity was initially linked to seven acetogenins that were further purified, and their dose-dependent effects in the presence of various agonists were contrasted. This process led to the identification of Persenone-C (3) as the most potent antiplatelet acetogenin (IC₅₀=3.4 mM) among the evaluated compounds. In vivo evaluations with Persenone A (4) demonstrated potential protective effects against arterial thrombosis (25 mg kg⁻¹ of body weight), as coagulation times increased (2-fold with respect to the vehicle) and thrombus formation was attenuated (71% versus vehicle). From these results, avocado may be referred to as a functional food containing acetogenin compounds that inhibit platelet aggregation with a potential preventive effect on thrombus formation, such as those that occur in ischaemic diseases. PMID:25319210

  15. Bacterial mutagenicity and chemical analysis of polycyclic aromatic hydrocarbons and some nitro derivatives in environmental samples collected in West Germany

    SciTech Connect

    Garner, R.C.; Stanton, C.A.; Martin, C.N.; Chow, F.L.; Thomas, W.; Hubner, D.; Herrmann, R.

    1986-01-01

    Snow and air particulate samples collected in Upper Frankonia, Federal Republic of Germany, have been analyzed for nitro-polycyclic aromatic hydrocarbons (PAH) and PAH content. A novel clean-up technique has been developed enabling interfering organochlorine environmental contaminants to be removed prior to analysis of the hydrocarbons by GC-MS. Mass fragmentation patterns are presented for 1-nitropyrene, 6-nitrobenzo(a)pyrene, 6-nitrochrysene, and 3-nitrofluoranthene. The level of these compounds found in air samples was in the range of 0.2-2.0 ng.m-3 with the exception of 6-nitrobenzo(a)pyrene, which was not detected. This compares with PAH values of between 1 and 6 ng.m-3. The freshly fallen snow sample collected at the side of a motorway had no detectable PAHs or nitro-PAHs. Parallel studies on the bacterial mutagenicity of the collected air samples using Salmonella typhimurium TA98 and TA100 in the presence and absence of aroclor-induced rat liver S9 revealed both direct and indirect activity. Larger numbers of mutants were induced in the presence of S9 than in its absence. The snow sample was devoid of mutagenic activity. These studies show the utility of the biological approach to screen environmental samples prior to expensive and time-consuming chemical analysis.

  16. Effects of lithium doping on microstructure, electrical properties, and chemical bonds of sol-gel derived NKN thin films

    SciTech Connect

    Lin, Chun-Cheng; Chen, Chan-Ching; Weng, Chung-Ming; Chu, Sheng-Yuan; Tsai, Cheng-Che

    2015-02-28

    Highly (100/110) oriented lead-free Li{sub x}(Na{sub 0.5}K{sub 0.5}){sub 1−x}NbO{sub 3} (LNKN, x = 0, 0.02, 0.04, and 0.06) thin films are fabricated on Pt/Ti/SiO{sub 2}/Si substrates via a sol-gel processing method. The lithium (Li) dopants modify the microstructure and chemical bonds of the LNKN films, and therefore improve their electrical properties. The optimal values of the remnant polarization (P{sub r} = 14.3 μC/cm{sup 2}), piezoelectric coefficient (d{sub 33} = 48.1 pm/V), and leakage current (<10{sup −5} A/cm{sup 2}) are obtained for a lithium addition of x = 0.04 (i.e., 4 at. %). The observation results suggest that the superior electrical properties are the result of an improved crystallization, a larger grain size, and a smoother surface morphology. It is shown that the ion transport mechanism is dominated by an Ohmic behavior under low electric fields and the Poole-Frenkel emission effect under high electric fields.

  17. Dislocation substructure of mantle-derived olivine as revealed by selective chemical etching and transmission electron microscopy

    USGS Publications Warehouse

    Kirby, S.H.; Wegner, M.W.

    1978-01-01

    Cleaved and mechanically polished surfaces of olivine from peridotite xenoliths from San Carlos, Arizona, were chemically etched using the techniques of Wegner and Christie (1974). Dislocation etch pits are produced on all surface orientations and they tend to be preferentially aligned along the traces of subgrain boundaries, which are approximately parallel to (100), (010), and (001). Shallow channels were also produced on (010) surfaces and represent dislocations near the surface that are etched out along their lengths. The dislocation etch channel loops are often concentric, and emanate from (100) subgrain boundaries, which suggests that dislocation sources are in the boundaries. Data on subgrain misorientation and dislocation line orientation and arguments based on subgrain boundary energy minimization are used to characterize the dislocation structures of the subgrain boundaries. (010) subgrain boundaries are of the twist type, composed of networks of [100] and [001] screw dislocations. Both (100) and (001) subgrain boundaries are tilt walls composed of arrays of edge dislocation with Burgers vectors b=[100] and [001], respectively. The inferred slip systems are {001} ???100???, {100} ???001???, and {010} ???100??? in order of diminishing importance. Exploratory transmission electron microscopy is in accord with these identifications. The flow stresses associated with the development of the subgrain structure are estimated from the densities of free dislocations and from the subgrain dimensions. Inferred stresses range from 35 to 75 bars using the free dislocation densities and 20 to 100 bars using the subgrain sizes. ?? 1978 Springer-Verlag.

  18. Sindbis virus as a tool for quality control of viral inactivation of heated and chemically treated plasma-derived products.

    PubMed

    Espíndola, Otávio M; Belluci, Marius S P; Oliveira, Barbara C E P D; Liberto, Maria Isabel M; Cabral, Maulori C

    2006-06-01

    Regulatory guidelines for production of plasma-derived products emphasize the need to document methods of viral inactivation and demonstrate the effectiveness of screening methods. Therefore, it is important to evaluate the kinetics of such processes. Togaviridae family virions may be considered as good tools for quality control of haemoderivatives, if they possess large amounts of cholesterol and saturated lipids and high structural lipid/protein ratio in their envelope composition, which give more resistance to classical treatments. The purpose of this study was to evaluate the efficiency of solvent-detergent and heat treatments adopted during the human haemoderivatives processment. Sindbis virus was used as a model for inactivation of enveloped viruses. Semi-processed human factor VIII (FVIII) product experimentally contaminated with Sindbis virus was used to test a solvent-detergent treatment with tri-N-butyl-phosphate (TNBP) and Tween 80. To evaluate thermal inactivation kinetics, lyophilized, and reconstituted samples of Sindbis virus-containing FVIII were incubated up to 30 h at 60 degrees C. The results showed that treatment with TNBP and Tween 80 reduced the infectivity of virus-contaminated FVIII in > or =5.5 log(10) and heat treatment was effective in all samples, although FVIII concentrate had reduced the rate of viral inactivation during a brief period of time. PMID:16507321

  19. Physico-chemical characterization of polymeric micelles loaded with platinum derivatives by capillary electrophoresis and related methods.

    PubMed

    Oukacine, Farid; Bernard, Stephane; Bobe, Iulian; Cottet, Hervé

    2014-12-28

    (1,2-diamino-cyclohexane)Platinum(II) ((DACH)Pt) loaded polymeric micelles of poly(ethylene glycol-b-sodium glutamate) (PEG-b-PGlu) are currently studied as a potential candidate to replace oxaliplatin in the treatment of cancers with the aim to reduce side effects like cumulative peripheral distal neurotoxicity and acute dysesthesias. As for all synthetic polymeric drug delivery systems, the characterization of the (co)polymer precursors and of the final drug delivery system (polymeric micelles) is crucial to control the repeatability of the different batches and to get correlation between physico-chemical structure and biological activity. In this work, the use of capillary electrophoresis (CE) and related methods for the characterization of (DACH)Pt-loaded polymeric micelles and their precursor (PEG-b-PGlu copolymer) has been investigated in detail. The separation and quantification of residual PGlu homopolymer in the PEG-b-PGlu sample were performed by free solution capillary zone electrophoresis mode. This mode brought also information on the PEG-b-PGlu copolymer composition and polydispersity. It also permitted to monitor the decomposition of polymeric micelles in the presence of NaCl at room temperature. Interactions between PEG-b-PGlu unimers, on one hand, and polymeric micelles or surfactants, on the other hand, were studied by using the Micellar Electrokinetic Chromatography and Frontal Analysis Capillary Electrophoresis modes. Finally, weight-average hydrodynamic radii of the loaded polymeric micelles and of the PEG-b-PGlu unimers were determined by Taylor Dispersion Analysis (an absolute size determination method that can be easily implemented on CE apparatus). PMID:25270114

  20. Chemical composition and cytotoxicity evaluation of essential oil from leaves of Casearia sylvestris, its main compound α-zingiberene and derivatives.

    PubMed

    Bou, Diego Dinis; Lago, João Henrique G; Figueiredo, Carlos R; Matsuo, Alisson L; Guadagnin, Rafael C; Soares, Marisi G; Sartorelli, Patricia

    2013-01-01

    Casearia sylvestris (Salicaceae), popularly known as "guaçatonga", is a plant widely used in folk medicine to treat various diseases, including cancer. The present work deals with the chemical composition as well as the cytotoxic evaluation of its essential oil, its main constituent and derivatives. Thus, the crude essential oil from leaves of C. sylvestris was obtained using a Clevenger type apparatus and analyzed by GC/MS. This analysis afforded the identification of 23 substances, 13 of which corresponded to 98.73% of the total oil composition, with sesquiterpene a-zingiberene accounting for 50% of the oil. The essential oil was evaluated for cytotoxic activity against several tumor cell lines, giving IC50 values ranging from 12 to 153 mg/mL. Pure a-zingiberene, isolated from essential oil, was also evaluated against the tumor cell lines showing activity for HeLa, U-87, Siha and HL60 cell lines, but with IC50 values higher than those determined for the crude essential oil. Aiming to evaluate the effect of the double bonds of a-zingiberene on the cytotoxic activity, partially hydrogenated a-zingiberene (PHZ) and fully hydrogenated a-zingiberene (THZ) derivatives were obtained. For the partially hydrogenated derivative only cytotoxic activity to the B16F10-Nex2 cell line (IC50 65 mg/mL) was detected, while totally hydrogenated derivative showed cytotoxic activity for almost all cell lines, with B16F10-Nex2 and MCF-7 as exceptions and with IC50 values ranging from 34 to 65 mg/mL. These results indicate that cytotoxic activity is related with the state of oxidation of compound. PMID:23966073

  1. Chemically primed bone-marrow derived mesenchymal stem cells show enhanced expression of chemokine receptors contributed to their migration capability

    PubMed Central

    Bidkhori, Hamid Reza; Ahmadiankia, Naghmeh; Matin, Maryam Moghaddam; Heirani-tabasi, Asieh; Farshchian, Moein; Naderi-meshkin, Hojjat; Shahriyari, Mina; Dastpak, Mahtab; Bahrami, Ahmad Reza

    2016-01-01

    Objective(s): The limited homing potential of bone-marrow-derived mesenchymal stem cells (BM-MSC) is the key obstacle in MSC-based therapy. It is believed that chemokines and chemokine receptor interactions play key roles in cellular processes associated with migration. Meanwhile, MSCs express a low level of distinct chemokine receptors and they even lose these receptors on their surface after a few passages which influence their therapeutic applications negatively. This study investigated whether treatment of BM-MSCs with hypoxia-mimicking agents would increase expression of some chemokine receptors and cell migration. Materials and Methods: BM-MSCs were treated at passage 2 for our gene expression profiling. All qPCR experiments were performed by SYBR Green method in CFX-96 Bio-Rad Real-Time PCR. The Boyden chamber assay was utilized to investigate BM-MSC homing. Results: Possible approaches to increasing the expression level of chemokine receptors by different hypoxia-mimicking agents such as valproic acid (VPA), CoCl2, and desferrioxamine (DFX) are described. Results show DFX efficiently up-regulate the CXCR7 and CXCR4 gene expression while VPA increase only the CXCR7 gene expression and no significant change in expression level of CXCR4 and the CXCR7 gene was detectable by CoCl2 treatment. Chemotaxis assay results show that pre-treatment with DFX, VPA, and Cocl2 enhances significantly the migration ability of BM-MSCs compared with the untreated control group and DFX treatment accelerates MSCs homing significantly with a higher rate than VPA and Cocl2 treatments. Conclusion: Our data supports the notion that pretreatment of MSC with VPA and DFX improves the efficiency of MSC therapy by triggering homing regulatory signaling pathways.

  2. Quantitative Spatiotemporal Chemical Profiling of Individual Lipid Droplets by Hyperspectral CARS Microscopy in Living Human Adipose-Derived Stem Cells.

    PubMed

    Di Napoli, Claudia; Pope, Iestyn; Masia, Francesco; Langbein, Wolfgang; Watson, Pete; Borri, Paola

    2016-04-01

    There is increasing evidence showing that cytosolic lipid droplets, present in all eukaryotic cells, play a key role in many cellular functions. Yet their composition at the individual droplet level and how it evolves over time in living cells is essentially unknown due to the lack of suitable quantitative nondestructive measurement techniques. In this work, we demonstrate the ability of label-free hyperspectral coherent anti-Stokes Raman scattering (CARS) microscopy, together with a quantitative image analysis algorithm developed by us, to quantify the lipid type and content in vol/vol concentration units of individual lipid droplets in living human adipose-derived stem cells during differentiation over 9 days in media supplemented with different fatty acids. Specifically, we investigated the addition of the polyunsaturated linoleic and alpha-linolenic fatty acids into the normal differentiation medium (mostly containing monounsaturated fatty acids). We observe a heterogeneous uptake which is droplet-size dependent, time dependent, and lipid dependent. Cells grown in linoleic-acid-supplemented medium show the largest distribution of lipid content across different droplets at all times during differentiation. When analyzing the average lipid content, we find that adding linoleic or alpha-linolenic fatty acids at day 0 results in uptake of the new lipid components with an exponential time constant of 22 ± 2 h. Conversely, switching lipids at day 3 results in an exponential time constant of 60 ± 5 h. These are unprecedented findings, exemplifying that the quantitative imaging method demonstrated here could open a radically new way of studying and understanding cytosolic lipid droplets in living cells. PMID:26937957

  3. Study of chemical reactivity in relation to experimental parameters of efficiency in coumarin derivatives for dye sensitized solar cells using DFT.

    PubMed

    Soto-Rojo, Rody; Baldenebro-López, Jesús; Glossman-Mitnik, Daniel

    2015-06-01

    A group of dyes derived from coumarin was studied, which consisted of nine molecules using a very similar manufacturing process of dye sensitized solar cells (DSSCs). Optimized geometries, energy levels of the highest occupied molecular orbital and the lowest unoccupied molecular orbital, and ultraviolet-visible spectra were obtained using theoretical calculations, and they were also compared with experimental conversion efficiencies of the DSSC. The representation of an excited state in terms of natural transition orbitals (NTOs) was studied. Chemical reactivity parameters were calculated and correlated with the experimental data linked to the efficiency of the DSSC. A new proposal was obtained to design new molecular systems and to predict their potential use as a dye in DSSCs. PMID:25959071

  4. Microwave plasma enhanced chemical vapor deposition growth of few-walled carbon nanotubes using catalyst derived from an iron-containing block copolymer precursor.

    PubMed

    Wang, Peng; Lu, Jennifer; Zhou, Otto

    2008-05-01

    The microwave plasma enhanced chemical vapor deposition (MPECVD) method is now commonly used for directional and conformal growth of carbon nanotubes (CNTs) on supporting substrates. One of the shortcomings of the current process is the lack of control of the diameter and diameter distribution of the CNTs due to difficulties in synthesizing well-dispersed catalysts. Recently, block copolymer derived catalysts have been developed which offer the potential of fine control of both the size of and the spacing between the metal clusters. In this paper we report the successful growth of CNTs with narrow diameter distribution using polystyrene-block-polyferrocenylethylmethylsilane (PS-b-PFEMS) as the catalyst precursor. The study shows that higher growth pressure leads to better CNT growth. Besides the pressure, the effects on the growth of CNTs of the growth parameters, such as temperature and precursor gas ratio, are also studied. PMID:21825693

  5. In vitro antibacterial activity of sphaeropsidins and chemical derivatives toward Xanthomonas oryzae pv. oryzae, the causal agent of rice bacterial blight.

    PubMed

    Evidente, Antonio; Venturi, Vittorio; Masi, Marco; Degrassi, Giuliano; Cimmino, Alessio; Maddau, Lucia; Andolfi, Anna

    2011-12-27

    Sphaeropsidin A, the main phytotoxin produced by Diplodia cupressi, as well as the two natural analogues sphaeropsidins B and C and 14 derivatives obtained by chemical modifications were assayed for antibacterial activity against Xanthomonas oryzae pv. oryzae, Pseudomonas fuscovaginae, and Burkholderia glumae, the causal agents of severe bacterial rice diseases. The results showed a strong and specific activity of sphaeropsidin A against X. oryzae pv. oryzae, while no activity was observed against the other two pathogens. The results of structure-activity relationship studies showed that structural features important to impart this antibacterial activity are the presence of the C-7 carbonyl group and the hemiketalic lactone functionality. The C-13 vinyl group, the double bond of ring C, and/or the tertiary C-9 hydroxy group, as well as the pimarane arrangement of the tricylic carbon skeleton, were also important for the antibacterial activity. These findings may be useful in designing novel compounds for practical applications in agriculture. PMID:22124378

  6. Chemical solution deposition derived (001)-oriented epitaxial BiFeO{sub 3} thin films with robust ferroelectric properties using stoichiometric precursors (invited)

    SciTech Connect

    Zhang, Qi; Valanoor, Nagarajan; Standard, Owen

    2014-08-14

    Phase pure bismuth ferrite (BiFeO{sub 3}) thin films with (001)-oriented epitaxial structure are realized on lanthanum strontium manganite (La{sub 0.67}Sr{sub 0.33}MnO{sub 3}) buffered (001)-SrTiO{sub 3} substrates by chemical solution deposition. The annealing process is optimized such that a stoichiometric precursor can be used to accurately control the Bi:Fe ratio. Ferroelectric, dielectric, and resistive switching behaviours are investigated for 40 nm, 70 nm, and 150 nm BFO thin films. While the thinnest film (40 nm) shows very leaky loops, square and fully saturated polarization hysteresis loops are shown for the thicker films. The highest remanent polarization (2P{sub r} = 100 μC/cm{sup 2}) and relative dielectric constant (ε{sub r} = 613) are obtained in the 150 nm BFO thin film. High cycle fatigue tests show that the thick films are resistant to polarization fatigue. Piezoresponse force microscopy results show that the domain structure varies with thickness. Resistive switching and polarization mediated diode effects are also observed. These robust properties suggest that chemical solution deposition derived BiFeO{sub 3} thin films can offer a viable low cost alternative.

  7. Common Host-Derived Chemicals Increase Catches of Disease-Transmitting Mosquitoes and Can Improve Early Warning Systems for Rift Valley Fever Virus

    PubMed Central

    Tchouassi, David P.; Sang, Rosemary; Sole, Catherine L.; Bastos, Armanda D. S.; Teal, Peter E. A.; Borgemeister, Christian; Torto, Baldwyn

    2013-01-01

    Rift Valley fever (RVF), a mosquito-borne zoonosis, is a major public health and veterinary problem in sub-Saharan Africa. Surveillance to monitor mosquito populations during the inter-epidemic period (IEP) and viral activity in these vectors is critical to informing public health decisions for early warning and control of the disease. Using a combination of field bioassays, electrophysiological and chemical analyses we demonstrated that skin-derived aldehydes (heptanal, octanal, nonanal, decanal) common to RVF virus (RVFV) hosts including sheep, cow, donkey, goat and human serve as potent attractants for RVFV mosquito vectors. Furthermore, a blend formulated from the four aldehydes and combined with CO2-baited CDC trap without a light bulb doubled to tripled trap captures compared to control traps baited with CO2 alone. Our results reveal that (a) because of the commonality of the host chemical signature required for attraction, the host-vector interaction appears to favor the mosquito vector allowing it to find and opportunistically feed on a wide range of mammalian hosts of the disease, and (b) the sensitivity, specificity and superiority of this trapping system offers the potential for its wider use in surveillance programs for RVFV mosquito vectors especially during the IEP. PMID:23326620

  8. Chemical solution deposition derived (001)-oriented epitaxial BiFeO3 thin films with robust ferroelectric properties using stoichiometric precursors (invited)

    NASA Astrophysics Data System (ADS)

    Zhang, Qi; Valanoor, Nagarajan; Standard, Owen

    2014-08-01

    Phase pure bismuth ferrite (BiFeO3) thin films with (001)-oriented epitaxial structure are realized on lanthanum strontium manganite (La0.67Sr0.33MnO3) buffered (001)-SrTiO3 substrates by chemical solution deposition. The annealing process is optimized such that a stoichiometric precursor can be used to accurately control the Bi:Fe ratio. Ferroelectric, dielectric, and resistive switching behaviours are investigated for 40 nm, 70 nm, and 150 nm BFO thin films. While the thinnest film (40 nm) shows very leaky loops, square and fully saturated polarization hysteresis loops are shown for the thicker films. The highest remanent polarization (2Pr = 100 μC/cm2) and relative dielectric constant (ɛr = 613) are obtained in the 150 nm BFO thin film. High cycle fatigue tests show that the thick films are resistant to polarization fatigue. Piezoresponse force microscopy results show that the domain structure varies with thickness. Resistive switching and polarization mediated diode effects are also observed. These robust properties suggest that chemical solution deposition derived BiFeO3 thin films can offer a viable low cost alternative.

  9. Computational and Experimental Assessment of Benzene Cation Chemistry for the Measurement of Marine Derived Biogenic Volatile Organic Compounds with Chemical Ionization Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Zoerb, M.; Kim, M.; Zimmermann, K.; Bertram, T. H.

    2013-12-01

    Chemical ionization mass spectrometry (CIMS) is a highly selective and sensitive technique for the measurement of trace gases in the atmosphere. However, competing side reactions and dependence on relative humidity (RH) can make the transition from the laboratory to the field challenging. Effective implementation of chemical ionization requires a thorough knowledge of the elementary steps leading to ionization of the analyte. We have recently investigated benzene cations for the detection of marine derived biogenic volatile organic compounds (BVOCs), such isoprene and terpene compounds, from algal bloom events. Our experimental results indicate that benzene ion chemistry is an attractive candidate for field measurements, and the RH dependence is weak. To further understand the advantages and limitations of this approach, we have also used electronic structure theory calculations to compliment the experimental work. These theoretical methods can provide valuable insight into the physical chemistry of ion molecule reactions including thermodynamical information, the stability of ions to fragmentation, and potential sources of interference such as dehydration to form isobaric ions. The combined experimental and computational approach also allows validation of the theoretical methods and will provide useful information towards gaining predictive power for the selection of appropriate reagent ions for future experiments.

  10. Quantum chemical investigation and statistical analysis of the relationship between corrosion inhibition efficiency and molecular structure of xanthene and its derivatives on mild steel in sulphuric acid

    NASA Astrophysics Data System (ADS)

    Obi-Egbedi, N. O.; Obot, I. B.; El-Khaiary, Mohammad I.

    2011-09-01

    A density functional theory (DFT) study of xanthene (XEN) and two of its derivatives namely xanthone (XAN) and xanthione (XION) recently used as corrosion inhibitors for mild steel in 0.5 M H 2SO 4 was undertaken at the B3LYP/631G (d) level. Inhibition efficiency obtained experimentally followed the order: XEN < XAN < XION. It was found that when the organic molecules adsorbed on the steel surface, molecular structure influences their interaction mechanism and by extension their inhibition efficiencies. The quantum chemical properties/descriptors most relevant to their potential action as corrosion inhibitors have been calculated in the neutral and protonated forms in aqueous phase for comparison. They include: Total energy (TE), EHOMO, ELUMO, energy gap (Δ E), dipole moment ( D), molecular area (MA), molecular volume (MV), hardness (η), softness ( σ˙), the fractions of electrons transferred (Δ N), electrophilicity index (ω) and total energy change (Δ ET). The quantum chemical parameters/descriptors were correlated with inhibition effect of the three inhibitors and were further used to explain the electron transfer mechanism between the inhibitors and the steel surface. Furthermore, equations were proposed using the non-linear and the multiple-linear regression analysis. The theoretical obtained results were found to be consistent with the experimental data reported.

  11. Common host-derived chemicals increase catches of disease-transmitting mosquitoes and can improve early warning systems for Rift Valley fever virus.

    PubMed

    Tchouassi, David P; Sang, Rosemary; Sole, Catherine L; Bastos, Armanda D S; Teal, Peter E A; Borgemeister, Christian; Torto, Baldwyn

    2013-01-01

    Rift Valley fever (RVF), a mosquito-borne zoonosis, is a major public health and veterinary problem in sub-Saharan Africa. Surveillance to monitor mosquito populations during the inter-epidemic period (IEP) and viral activity in these vectors is critical to informing public health decisions for early warning and control of the disease. Using a combination of field bioassays, electrophysiological and chemical analyses we demonstrated that skin-derived aldehydes (heptanal, octanal, nonanal, decanal) common to RVF virus (RVFV) hosts including sheep, cow, donkey, goat and human serve as potent attractants for RVFV mosquito vectors. Furthermore, a blend formulated from the four aldehydes and combined with CO(2)-baited CDC trap without a light bulb doubled to tripled trap captures compared to control traps baited with CO(2) alone. Our results reveal that (a) because of the commonality of the host chemical signature required for attraction, the host-vector interaction appears to favor the mosquito vector allowing it to find and opportunistically feed on a wide range of mammalian hosts of the disease, and (b) the sensitivity, specificity and superiority of this trapping system offers the potential for its wider use in surveillance programs for RVFV mosquito vectors especially during the IEP. PMID:23326620

  12. Continuous water infusion enhances atmospheric pressure chemical ionization of methyl chloroformate derivatives in gas chromatography coupled to time-of-flight mass spectrometry-based metabolomics.

    PubMed

    Wachsmuth, Christian J; Dettmer, Katja; Lang, Sven A; Mycielska, Maria E; Oefner, Peter J

    2014-09-16

    The effects of continuous water infusion on efficiency and repeatability of atmospheric pressure chemical ionization of both methyl chloroformate (MCF) and methoxime-trimethylsilyl (MO-TMS) derivatives of metabolites were evaluated using gas chromatography-time-of-flight mass spectrometry. Water infusion at a flow-rate of 0.4 mL/h yielded not only an average 16.6-fold increase in intensity of the quasimolecular ion for 20 MCF-derivatized metabolite standards through suppression of in-source fragmentation but also the most repeatable peak area integrals. The impact of water infusion was the greatest for dicarboxylic acids and the least for (hetero-) aromatic compounds. Water infusion also improved the ability to detect reliably fold changes as small as 1.33-fold for the same 20 MCF-derivatized metabolite standards spiked into a human serum extract. On the other hand, MO-TMS derivatives were not significantly affected by water infusion, neither in their fragmentation patterns nor with regard to the detection of differentially regulated compounds. As a proof of principle, we applied MCF derivatization and GC-APCI-TOFMS to the detection of changes in abundance of metabolites in pancreatic cancer cells upon treatment with 17-DMAG. Water infusion increased not only the number of metabolites identified via their quasimolecular ion but also the reproducibility of peak areas, thereby almost doubling the number of significantly regulated metabolites (false discovery rate < 0.05) to a total of 23. PMID:25152309

  13. Lead and copper immobilization in a shooting range soil using soybean stover- and pine needle-derived biochars: Chemical, microbial and spectroscopic assessments.

    PubMed

    Ahmad, Mahtab; Ok, Yong Sik; Rajapaksha, Anushka Upamali; Lim, Jung Eun; Kim, Byung-Yong; Ahn, Jae-Hyung; Lee, Young Han; Al-Wabel, Mohammad I; Lee, Sung-Eun; Lee, Sang Soo

    2016-01-15

    Biochar (BC) could be a potential candidate for the remediation of metal contaminated soil. Mechanistic understandings are needed for the appropriate selection of BC and investigating molecular microbial ecological interactions. The soybean stover-derived BCs were more effective in immobilizing Pb (88%) and Cu (87%) than the pine needle-derived BCs in a contaminated shooting range soil. The sequential chemical extractions indicated that BCs stimulated the geochemical transformation of metal species. Spectroscopic investigations using scanning electron microscopic elemental dot mapping and extended X-ray absorption fine structure spectroscopic measurements showed that Pb in the BCs amended soils was immobilized by the formation of stable chloropyromorphite. Soil organic C and microbial activity were also enhanced by BC. The non-labile C fraction in the soil amended with BCs produced at 700°C was increased. Biochars showed less impact on the bacterial community than feedstock biomass as promulgated by the pyrosequencing of 16S rRNA gene. The feedstock type (namely soybean stover and pine needles) was the main factor influencing the BCs efficacy on metals' (im) mobilization and bacterial health in soils. PMID:26355413

  14. Adding liraglutide to the backbone therapy of biguanide in patients with coronary artery disease and newly diagnosed type-2 diabetes (the AddHope2 study): a randomised controlled study protocol

    PubMed Central

    Anholm, Christian; Kumarathurai, Preman; Klit, Malene S; Kristiansen, Ole P; Nielsen, Olav W; Ladelund, Steen; Madsbad, Sten; Sajadieh, Ahmad; Haugaard, Steen B

    2014-01-01

    Introduction Newly diagnosed type 2 diabetes mellitus (T2DM) in patients with coronary artery disease (CAD) more than doubles the risk of death compared with otherwise matched glucose tolerant patients. The biguanide metformin is the drug of choice in treatment of T2DM and has shown to ameliorate cardiovascular morbidity in patients with T2DM and myocardial infarction (MI). The incretin hormone, glucagon-like peptide-1 (GLP-1) improves β-cell function, insulin sensitivity and causes weight loss and has been suggested to have beneficial effects on cardiac function. The GLP-1 receptor agonist (GLP-1RA), liraglutide, is currently used for treatment of T2DM but its potential effect on cardiac function has not been investigated in detail. We hypothesised that liraglutide added to metformin backbone therapy in patients with CAD and newly diagnosed T2DM will improve β-cell function and left ventricular systolic function during dobutamine stress. Methods and analyses 40 patients with CAD and newly diagnosed T2DM will receive the intervention liraglutide+metformin and placebo+metformin in this investigator-initiated, double blind, randomised, placebo-controlled, cross-over 12 plus 12 weeks intervention study with a 2-week washout period. The primary cardiovascular end point is changes in left ventricular ejection fraction during stress echocardiography. The primary endocrine end point is β-cell function evaluated during a frequently sampled intravenous glucose tolerance test. Secondary end points include heart rate variability, diurnal blood pressure, glucagon suppression and inflammatory response (urine, blood and adipose tissue). Ethics and dissemination This study is approved by the Danish Medicines Agency, the Danish Dataprotection Agency and the Regional Committee on Biomedical Research Ethics of the Capital Region of Denmark. The trial will be carried out under the guidance from the GCP unit at Copenhagen University Hospital of Bispebjerg and in accordance with the ICH-GCP guidelines and the Helsinki Declaration. Trial registrations number Clinicaltrials.gov ID: NCT01595789, EudraCT: 2011-005405-78. PMID:25031198

  15. Sol-gel-derived NiO/NiAl{sub 2}O{sub 4} oxygen carriers for chemical-looping combustion by coal char

    SciTech Connect

    Haibo Zhao; Liming Liu; Baowen Wang; Di Xu; Linlin Jiang; Chuguang Zheng

    2008-03-15

    This paper focuses on the investigation of Ni-based oxygen carriers for CLC by coal char. First, Al(OC{sub 3}H{sub 7}){sub 3} and Ni(NO{sub 3}){sub 2} are selected as the main raw materials to prepare sol-gel-derived NiO/NiAl{sub 2}O{sub 4} oxygen carriers. The oxygen carrier with a mass content of 60% NiO, a sintering temperature of 1300{sup o}C, and a sintering time of 6 h performs comparatively well. Second, the reduction reaction of the NiO/NiAl{sub 2}O{sub 4} oxygen carriers with char and the circular reduction/oxidation reactions of the NiO/NiAl{sub 2}O{sub 4} oxygen carriers with char/air or hydrogen/air are carried out in a thermogravimetric analysis (TGA) instrument to investigate the reactivities and chemical life of the prepared NiO/NiAl{sub 2}O{sub 4} oxygen carriers. The experimental results show that (a) when the TGA temperature is higher than 850{sup o}C, NiO/NiAl{sub 2}O{sub 4} starts to react with coal char rapidly, which indicates that CLC of coal char using NiO/NiAl{sub 2}O{sub 4} as oxygen carriers is a feasible technology of energy utilization in principle; (b) NiO/NiAl{sub 2}O{sub 4}, which maintains its activity over single-cycle reduction/oxidation reactions with char/air or multiple-cycle reduction/oxidation reactions with hydrogen/air, exhibits extremely good recyclablity; (c) the porous beehive structure of the NiO/NiAl{sub 2}O{sub 4} particle is maintained, and the sintering behavior between different particles is not observed during cyclic studies. Those experimental results prove the sol-gel-derived oxygen carrier NiO/NiAl{sub 2}O{sub 4} is capable of being used in chemical-looping combustion fueled by coal char or H{sub 2}. 51 refs., 5 figs., 5 tabs.

  16. Chemical activation in Rhinella arenarum oocytes: effect of dehydroleucodine (DhL) and its hydrogenated derivative (2H-DhL).

    PubMed

    Medina, M F; Bühler, M I; Sánchez-Toranzo, G

    2015-12-01

    Mature oocytes are arrested in metaphase II due to the presence of high levels of active maturation promoting factor (MPF). After fertilization, active MPF levels decline abruptly, enabling oocytes to complete meiosis II. One of the first and universal events of oocyte activation is an increase in cytosolic Ca2+ that would be responsible for MPF inactivation. Mature oocytes can also be activated by parthenogenetic activation. The aims of this work are to test the ability of dehydroleucodine (DhL) and its hydrogenated derivative 11,13-dihydro-dehydroleucodine (2H-DhL) to induce chemical activation in amphibian oocytes and to study the participation of calcium in the process. Results indicated that DhL and 2H-DhL induced oocyte activation in a dose-dependent manner. After 90 min of treatment, DhL 36 μM was able to induce 95% activation, while 2H-DhL 36 μM was less active, with only 40% activation. Our results suggest that DhL induced the inhibition of MPF activity, probably by an increase in intracellular Ca2+ concentration. Extracellular Ca2+ would not be significant, although Ca2+ release from intracellular stores is critical. In this sense, IP3Rs and RyRs were involved in the Ca2+ transient induced by lactones. In this species, RyRs appears to be the largest contributor to Ca2+ release in DhL-induced activation. Although more studies are needed on the mechanism of action through which these lactones induce oocyte activation in Rhinella arenarum, the results of this research provide interesting perspectives for the use of these lactones as chemical activators in in vitro fertilization and cloning. PMID:25424172

  17. Cross-shelf and along-shelf nutrient fluxes derived from flow fields and chemical hydrography observed in the southern East China Sea off northern Taiwan

    NASA Astrophysics Data System (ADS)

    Liu, Kon-Kee; Yung Tang, Tswen; Gong, Gwo-Ching; Chen, Liang-Yu; Shiah, Fuh-Kwo

    2000-03-01

    Cross-shelf exchange of nutrients (N, P and Si) off northeastern Taiwan and along-shelf transports just north of the Taiwan Strait was assessed using chemical hydrography and velocity fields observed in August 1994 (summer) and March 1997 (winter). The summer survey was conducted along the periphery of a triangle. The velocity field was determined by phase-averaged current velocities measured with ship-borne ADCP on two rounds separated by 3.5 cycles of the dominant M 2 tide. Nutrient distributions were derived from phase-averaged hydrographic data. Although the inflowing and outflowing volume transports were mismatched by 14% largely due to poorly estimated surface flow that carried little nutrients, the inputs and outputs of nutrients agreed within 2-5%. Such consistency lends support to the adopted approach for estimating nutrient fluxes. The winter survey, which provided observations on two transects, one along-shelf and one cross-shelf, was conducted using two ships separated by 1/2 cycle of the M 2 tide. Results from the two ships allowed determination of the phase-averaged flow fields and chemical hydrography. The two surveys indicated that the Kuroshio upwelling provided rather constant nutrient fluxes to the shelf, which were comparable to the total nutrient influxes from slope waters to the Mid and South Atlantic Bight and considerably larger than the riverine sources. Significant amounts of nutrients from the shelf leaked back into the surface layer of the Kuroshio, replenishing its impoverished nutrient reserves. Along-shelf nutrient fluxes from the Taiwan Strait changed drastically between seasons, ranging from less than half to more than double the Kuroshio inputs. In the light of the variability of the shelf environment, more observations are needed to better determine the mean condition of this transport.

  18. The Chemically Synthesized Ageladine A-Derivative LysoGlow84 Stains Lysosomes in Viable Mammalian Brain Cells and Specific Structures in the Marine Flatworm Macrostomum lignano

    PubMed Central

    Mordhorst, Thorsten; Awal, Sushil; Jordan, Sebastian; Petters, Charlotte; Sartoris, Linda; Dringen, Ralf; Bickmeyer, Ulf

    2015-01-01

    Based on the chemical structure and the known chemical synthesis of the marine sponge alkaloid ageladine A, we synthesized the ageladine A-derivative 4-(naphthalene-2-yl)-1H-imidazo[4,5-c]pyridine trifluoroacetate (LysoGlow84). The two-step synthesis started with the Pictet-Spengler reaction of histamine and naphthalene-2-carbaldehyde to a tetrahydropyridine intermediate, which was dehydrogenated with activated manganese (IV) oxide to LysoGlow84. Structure and purity of the synthesized LysoGlow84 were confirmed by NMR spectroscopy and mass spectrometry. The fluorescence intensity emitted by LysoGlow84 depended strongly on the pH of the solvent with highest fluorescence intensity recorded at pH 4. The fluorescence maximum (at 315 nm excitation) was observed at 440 nm. Biocompatibility of LysoGlow84 was investigated using cultured rat brain astrocytes and the marine flatworm Macrostomum lignano. Exposure of the astrocytes for up to 6 h to micromolar concentrations of LysoGlow84 did not compromise cell viability, as demonstrated by several viability assays, but revealed a promising property of this compound for staining of cellular vesicles. Conventional fluorescence microscopy as well as confocal scanning microscopy of LysoGlow84-treated astrocytes revealed co-localization of LysoGlow84 fluorescence with that of LysoTracker® Red DND-99. LysoGlow84 stained unclear structures in Macrostomum lignano, which were identified as lysosomes by co-staining with LysoTracker. Strong fluorescence staining by LysoGlow84 was further observed around the worms’ anterior gut and the female genital pore which were not counterstained by LysoTracker Red. Thus, LysoGlow84 is a new promising dye that stains lysosomes and other acidic compartments in cultured cells and in worms. PMID:25679913

  19. Chemical microsensors

    DOEpatents

    Li, DeQuan; Swanson, Basil I.

    1995-01-01

    An article of manufacture is provided including a substrate having an oxide surface layer and a selective thin film of a cyclodextrin derivative chemically bound upon said substrate, said film is adapted for the inclusion of a selected organic compound therewith. Such an article can be either a chemical sensor capable of detecting a resultant mass change from inclusion of the selected organic compound or a chemical separator capable of reversibly selectively separating a selected organic compound.

  20. VITAL NMR: Using Chemical Shift Derived Secondary Structure Information for a Limited Set of Amino Acids to Assess Homology Model Accuracy

    SciTech Connect

    Brothers, Michael C; Nesbitt, Anna E; Hallock, Michael J; Rupasinghe, Sanjeewa; Tang, Ming; Harris, Jason B; Baudry, Jerome Y; Schuler, Mary A; Rienstra, Chad M

    2011-01-01

    Homology modeling is a powerful tool for predicting protein structures, whose success depends on obtaining a reasonable alignment between a given structural template and the protein sequence being analyzed. In order to leverage greater predictive power for proteins with few structural templates, we have developed a method to rank homology models based upon their compliance to secondary structure derived from experimental solid-state NMR (SSNMR) data. Such data is obtainable in a rapid manner by simple SSNMR experiments (e.g., (13)C-(13)C 2D correlation spectra). To test our homology model scoring procedure for various amino acid labeling schemes, we generated a library of 7,474 homology models for 22 protein targets culled from the TALOS+/SPARTA+ training set of protein structures. Using subsets of amino acids that are plausibly assigned by SSNMR, we discovered that pairs of the residues Val, Ile, Thr, Ala and Leu (VITAL) emulate an ideal dataset where all residues are site specifically assigned. Scoring the models with a predicted VITAL site-specific dataset and calculating secondary structure with the Chemical Shift Index resulted in a Pearson correlation coefficient (-0.75) commensurate to the control (-0.77), where secondary structure was scored site specifically for all amino acids (ALL 20) using STRIDE. This method promises to accelerate structure procurement by SSNMR for proteins with unknown folds through guiding the selection of remotely homologous protein templates and assessing model quality.

  1. Stabilization of asphaltenes in aliphatic solvents using alkylbenzene-derived amphiphiles. 1. Effect of the chemical structure of amphiphiles on asphaltene stabilization

    SciTech Connect

    Chang, C.L.; Fogler, H.S. )

    1994-06-01

    Stabilization of crude oil asphaltenes in apolar alkane solvents was investigated using a series of alkylbenzene-derived amphiphiles as the asphaltene stabilizers. In this paper (i.e., part I), we present the study on the influences of the chemical structure of these amphiphiles on the effectiveness of asphaltene solubilization and on the strength of asphaltene-amphiphile interaction using both UV/vis and FTIR spectroscopies. The results showed that the amphiphile's effectiveness of asphaltene stabilization was primarily controlled by the polarity of the amphiphile's head group and the length of the amphiphile's alkyl tail. Increasing the acidity of the amphiphile's head group could promote the amphiphile's ability to stabilize asphaltenes by increasing the acid-base attraction between asphaltenes and amphiphiles. On the other hand, although decreasing the amphiphile's tail length increased the asphaltene-amphiphile attraction slightly, it still required a minimum tail length (six carbons for p-alkylphenol amphiphiles) for amphiphiles to form stable steric layers around asphaltenes. We also found additional acidic side groups of amphiphiles could further improve the amphiphile's ability to stabilize asphaltenes. The effect of the molecular weight of alkane solvents on the amphiphile's ability to stabilize asphaltenes was also studied. 18 refs., 12 figs., 3 tabs.

  2. HL271, a novel chemical compound derived from metformin, differs from metformin in its effects on the circadian clock and metabolism.

    PubMed

    Row, Hansang; Jeong, Jaekap; Cho, Sehyung; Kim, Sungwuk; Kim, Kyungjin

    2016-01-15

    Metformin is a treatment of choice for patients with type 2 diabetes. Its action involves the phosphorylation of 5'-adenosine monophosphate activated protein kinase (AMPK), leading to inhibition of liver gluconeogenesis. The effects of a novel chemical compound derived from metformin, HL271, on molecular and physiological actions involving AMPK and rhythmically-expressed circadian clock genes were investigated. HL271 potently activated AMPK in a dose-dependent manner, and produced shortening of the circadian period and enhanced degradation of the clock genes PER2 and CRY1. Although the molecular effects of HL271 resembled those of metformin, it produced different physiological effects in mice with diet-induced obesity. HL271 did not elicit glucose-lowering or insulin-sensitizing effects, possibly because of altered regulation of glucose-6-phosphatase and phosphoenolpyruvate carboxykinase 1. This indicated that, although HL271 acted on circadian clock machinery through a similar molecular mechanism to metformin, it differed in its systemic effect on glucose and lipid metabolite regulations. PMID:26707879

  3. Upgrading oxygenated Fischer-Tropsch derivatives and one-step direct synthesis of ethyl acetate from ethanol - examples of the desirability of research on simple chemical compounds transformations.

    PubMed

    Klimkiewicz, Roman

    2014-01-01

    Oxygenates formed as by-products of Fischer-Tropsch syntheses can be transformed into other Fischer-Tropsch derived oxygenates instead of treating them as unwanted chemicals. One-step direct synthesis of ethyl acetate from ethanol is feasible with the use of some heterogeneous catalysts. Despite their apparent simplicity, both transformations are discussed as targeted fields of research. Furthermore, the two concepts are justified due to the environmental protection. Arguments regarding the Fischer-Tropsch process are focused on the opportunities of the utilization of undesirable by-products. The effective striving for their utilization can make the oxygenates the targeted products of this process. Arguments regarding the one-step direct synthesis of ethyl acetate underline the environmental protection and sustainability as a less waste-generating method but, above all, highlight the possibility of reducing the glycerol overproduction problem. The production of ethyl acetate from bioethanol and then transesterification of fats and oils with the use of ethyl acetate allows managing all the renewable raw materials. Thus, the process enables the biosynthesis of biodiesel without glycerine by-product and potentially would result in the increase in the demand for ethyl acetate. Graphical Abstract. PMID:25648719

  4. Effect of hydrogen sulfide on chemical looping combustion of coal-derived synthesis gas over bentonite-supported metal-oxide oxygen carriers

    SciTech Connect

    Tian, H.J.; Simonyi, T.; Poston, J.; Siriwardane, R.

    2009-09-15

    The effect of hydrogen sulfide (H{sub 2}S) on the chemical looping combustion of coal-derived synthesis gas with bentonite-supported metal oxides - such as iron oxide, nickel oxide, manganese oxide, and copper oxide - was investigated by thermogravimetric analysis, mass spectrometry, and X-ray photoelectron spectroscopy (XPS). During the reaction with synthesis gas containing H{sub 2}S, metal-oxide oxygen carriers were first reduced by carbon monoxide and hydrogen, and then interacted with H{sub 2}S to form metal sulfide, which resulted in a weight gain during the reduction/sulfidation step. The reduced/sulfurized compounds could be regenerated to form sulfur dioxide and oxides during the oxidation reaction with air. The reduction/oxidation capacities of iron oxide and nickel oxide were not affected by the presence of H{sub 2}S, but both manganese oxide and copper oxide showed decreased reduction/oxidation capacities. However, the rates of reduction and oxidation decreased in the presence of H{sub 2}S for all four metal oxides.

  5. Effect of hydrogen sulfide on chemical looping of coal-derived synthesis gas over bentonite-supported metal---oxide oxygen carriers

    SciTech Connect

    Tian, H.; Simonyi, T.; Poston, J.; Siriwardane, R.

    2009-01-01

    The effect of hydrogen sulfide (H2S) on the chemical looping combustion of coal-derived synthesis gas with bentonite-supported metal oxidesssuch as iron oxide, nickel oxide, manganese oxide, and copper oxideswas investigated by thermogravimetric analysis, mass spectrometry, and X-ray photoelectron spectroscopy (XPS). During the reaction with synthesis gas containing H2S, metal-oxide oxygen carriers were first reduced by carbon monoxide and hydrogen, and then interacted with H2S to form metal sulfide, which resulted in a weight gain during the reduction/sulfidation step. The reduced/sulfurized compounds could be regenerated to form sulfur dioxide and oxides during the oxidation reaction with air. The reduction/oxidation capacities of iron oxide and nickel oxide were not affected by the presence of H2S, but both manganese oxide and copper oxide showed decreased reduction/oxidation capacities. However, the rates of reduction and oxidation decreased in the presence of H2S for all four metal oxides.

  6. Comparative investigation on chemical looping combustion of coal-derived synthesis gas containing H2S over supported NiO oxygen carriers

    SciTech Connect

    Ksepko, E.; Siriwardane, R.; Tian, H.; Simonyi, T.; Sciazko, M.

    2010-01-01

    Chemical looping combustion (CLC) of simulated coal-derived synthesis gas was conducted with NiO oxygen carriers supported on SiO2, ZrO2, TiO2, and sepiolite. The effect of H2S on the performance of these samples for the CLC process was also evaluated. Five-cycle thermogravimetric analysis (TGA) tests at 800 #1;C indicated that all oxygen carriers had a stable performance at 800 #1;C, except NiO/SiO2. Full reduction/oxidation reactions of the oxygen carrier were obtained during the five-cycle test. It was found that support had a significant effect on reaction performance of NiO both in reduction and oxidation rates. The reduction reaction was significantly faster than the oxidation reaction for all oxygen carriers, while the oxidation reaction is fairly slow due to oxygen diffusion on NiO layers. The reaction profile was greatly affected by the presence of H2S, but there was no effect on the capacity due to the presence of H2S in synthesis gas. The presence of H2S decreased reduction reaction rates significantly, but oxidation rates of reduced samples increased. X-ray diffraction (XRD) data of the oxidized samples after a five-cycle test showed stable crystalline phases without any formation of sulfides or sulfites/sulfates. Increase in reaction temperature to 900 #1;C had a positive effect on the performance.

  7. Three New and Eleven Known Unusual C25 Steroids: Activated Production of Silent Metabolites in a Marine-Derived Fungus by Chemical Mutagenesis Strategy using Diethyl Sulphate

    PubMed Central

    Xia, Ming-Wen; Cui, Cheng-Bin; Li, Chang-Wei; Wu, Chang-Jing

    2014-01-01

    Three new (1–3) and 11 known (4–14) C25 steroids with an unusual bicyclo[4.4.1]A/B ring system were isolated by tracing newly produced metabolites in the EtOAc extract of an antitumor mutant AD-1-2 obtained by the diethyl sulphate (DES) mutagenesis of a marine-derived Penicillium purpurogenum G59. HPLC-PDAD-UV and HPLC-ESI-MS analyses indicated that the G59 strain did not produce these metabolites and the production of 1–14 in the mutant AD-1-2 extract was caused by the activation of silent metabolites in the original G59 strain by DES mutagenesis. The structures of the new compounds, named antineocyclocitrinols A (1) and B (2) and 23-O-methylantineocyclocitrinol (3), including their absolute configurations were determined by various spectroscopic methods, especially the NMR and Mo2-induced CD analyses. Compounds 1–3 provide the first examples of the C25 bicyclo[4.4.1]A/B ring steroids with the Z-configuration of 20,22-double bond. All of 1–14 weakly inhibited several human cancer cell lines to varying extents. These results provided additional examples for the successful application of the chemical mutagenesis strategy using DES to discover new compounds by activating silent metabolites in fungal isolates and supported also the effectiveness and usefulness of this new strategy. PMID:24633254

  8. Chemical and genetic blockade of HDACs enhances osteogenic differentiation of human adipose tissue-derived stem cells by oppositely affecting osteogenic and adipogenic transcription factors

    SciTech Connect

    Maroni, Paola; Brini, Anna Teresa; Dipartimento di Scienze Biomediche, Chirurgiche ed Odontoiatriche, Universita degli Studi di Milano, Milano ; Arrigoni, Elena; Girolamo, Laura de; Niada, Stefania; Dipartimento di Scienze Biomediche, Chirurgiche ed Odontoiatriche, Universita degli Studi di Milano, Milano ; Matteucci, Emanuela; Bendinelli, Paola; Desiderio, Maria Alfonsina

    2012-11-16

    Highlights: Black-Right-Pointing-Pointer Acetylation affected hASCs osteodifferentiation through Runx2-PPAR{gamma}. Black-Right-Pointing-Pointer HDACs knocking-down favoured the commitment effect of osteogenic medium. Black-Right-Pointing-Pointer HDACs silencing early activated Runx2 and ALP. Black-Right-Pointing-Pointer PPAR{gamma} reduction and calcium/collagen deposition occurred later. Black-Right-Pointing-Pointer Runx2/PPAR{gamma} target genes were modulated in line with HDACs role in osteo-commitment. -- Abstract: The human adipose-tissue derived stem/stromal cells (hASCs) are an interesting source for bone-tissue engineering applications. Our aim was to clarify in hASCs the role of acetylation in the control of Runt-related transcription factor 2 (Runx2) and Peroxisome proliferator activated receptor (PPAR) {gamma}. These key osteogenic and adipogenic transcription factors are oppositely involved in osteo-differentiation. The hASCs, committed or not towards bone lineage with osteoinductive medium, were exposed to HDACs chemical blockade with Trichostatin A (TSA) or were genetically silenced for HDACs. Alkaline phosphatase (ALP) and collagen/calcium deposition, considered as early and late osteogenic markers, were evaluated concomitantly as index of osteo-differentiation. TSA pretreatment, useful experimental protocol to analyse pan-HDAC-chemical inhibition, and switch to osteogenic medium induced early-osteoblast maturation gene Runx2, while transiently decreased PPAR{gamma} and scarcely affected late-differentiation markers. Time-dependent effects were observed after knocking-down of HDAC1 and 3: Runx2 and ALP underwent early activation, followed by late-osteogenic markers increase and by PPAR{gamma}/ALP activity diminutions mostly after HDAC3 silencing. HDAC1 and 3 genetic blockade increased and decreased Runx2 and PPAR{gamma} target genes, respectively. Noteworthy, HDACs knocking-down favoured the commitment effect of osteogenic medium. Our results reveal a role for HDACs in orchestrating osteo-differentiation of hASCs at transcriptional level, and might provide new insights into the modulation of hASCs-based regenerative therapy.

  9. Predicting biological effects of environmental mixtures using exposure:activity ratios (EAR) derived from US EPA’s ToxCast data: Retrospective application to chemical monitoring data

    EPA Science Inventory

    Chemical monitoring has been widely used in environmental surveillance to assess exposure to environmental contaminants which could represent potential hazards to exposed organisms. However, the ability to detect chemicals in the environment has rapidly outpaced assessment of pot...

  10. Predicting biological effects of environmental mixtures using exposure:activity ratios (EAR) derived from US EPAs ToxCast data: Retrospective application to chemical monitoring data

    EPA Science Inventory

    Chemical monitoring has been widely used in environmental surveillance to assess exposure to environmental contaminants which could represent potential hazards to exposed organisms. However, the ability to detect chemicals in the environment has rapidly outpaced assessment of pot...

  11. A combination of 3D-QSAR, docking, local-binding energy (LBE) and GRID study of the species differences in the carcinogenicity of benzene derivatives chemicals.

    PubMed

    Fratev, Filip; Benfenati, Emilio

    2008-09-01

    A combination of 3D-QSAR, docking, local-binding energy (LBE) and GRID methods was applied as a tool to study and predict the mechanism of action of 100 carcinogenic benzene derivatives. Two 3D-QSAR models were obtained: (i) model of mouse carcinogenicity on the basis of 100 chemicals (model 1) and (ii) model of the differences in mouse and rat carcinogenicity on the basis of 73 compounds (model 2). 3D-QSAR regression maps indicated the important differences in species carcinogenicity, and the molecular positions associated with them. In order to evaluate the role of P450 metabolic process in carcinogenicity, the following approaches were used. The 3D models of CYP2E1 for mouse and rat were built up. A docking study was applied and the important ligand-protein residues interactions and oxidation positions of the molecules were identified. A new approach for quantitative assessment of metabolism pathways was developed, which enabled us to describe the species differences in CYP2E1 metabolism, and how it can be related to differences in the carcinogenic potential for a subset of compounds. The binding energies of the important substituents (local-binding energy-LBE) were calculated, in order to quantitatively demonstrate the contribution of the substituents in metabolic processes. Furthermore, a computational procedure was used for determining energetically favourable binding sites (GRID examination) of the enzymes. The GRID procedure allowed the identification of some important differences, related to species metabolism in CYP2E1. Comparing GRID, 3D-QSAR maps and LBE results, a similarity was identified, indicating a relationship between P450 metabolic processes and the differences in the carcinogenicity. PMID:18495507

  12. Constraints on the Origins of Along-Arc and Cross-Arc Chemical Variations in Arc Volcanic systems Derived from Global Systematics of Fluid-Mobile Elements

    NASA Astrophysics Data System (ADS)

    Ryan, Jeffrey

    2014-05-01

    The fluid-mobile element (FME) "clan" (B, Cs, As, Sb; conditionally Pb, Rb, Ba, Li, N, I: Leeman 1996; Noll et al 1996; Bebout et al 1999; Savov et al 2005) comprises a chemically disparate suite of trace elements that have in common evidence for low T°/low P mobility from subducting materials in H2O-dominated fluid species. The FME are highly variable in volcanic arc lavas, showing marked along-arc and across arc changes in nearly all of the arc volcanic systems that have been examined. Globally, along-arc variability of the FME can be explained as source mixing, with most arcs defining arrays between two predominant sources: the first a strongly FME-enriched endmember, showing enrichment patterns consistent with those observed in subduction-related serpentinites (Savov et al 2005; Hattori and Guillot 2007), and the second an FME-poor source with signatures for other large-ion lithophile elements (LIL) consistent with subducted slab (predominantly subducted sediment) derivation. The mantle is a negligible contributor to FME systematics in those arcs where the inferred thermal structures are cool at relatively shallow (30-40 km) depths (e.g., Syracuse, et al 2011). However, in the relatively few arcs that show hotter thermal structures at shallow depths, the FME-enriched component is absent, and the mixing components are the mantle and the FME-poor, LIL enriched component observed in all arcs. Regular across-arc declines in enrichments of boron and other FME are a diagnostic feature in volcanic arcs globally. B abundance and isotope systematics for across-arc transects point to a) anomalously high B and B isotope signals near the volcanic front, often some of the highest signatures in the arc, suggesting locally higher inputs of the FME-enriched endmember to mantle sources at that point along the volcanic front. These enrichments, as well as the positioning of the widest volcanic cross-chains, are often linked to physical phenomena (seamount or fracture zone subduction, or faults or grabens perpendicular to the strike of the arc). b) Along cross-arc arrays, there is FME evidence for three-component mixing, involving the two slab-derived FME components and the mantle, in which the FME-depleted slab endmember plays a greater role as subduction depths increase. In general, the overriding arc crust plays a minor role in the FME systematics of arcs, though in those cases where the crustal section is thick and slab-derived signatures are modest, the crustal contribution helps define a baseline level for FME abundance and isotopic signatures throughout the arc. References: Bebout, et al 1999, EPSL 177, 69; Hattori and Guillot, 2007, GCubed, http://dx.doi.org/10.1029/2007GC001594; Leeman. 1996, AGU Monograph 96, 269; Noll et al, 1996, GCA 60, 587; Savov et al, 2005; GCubed, Q04J15 DOI10.1029/2004GC000777; Syracuse et al. 2011, GCubed, http://dx.doi.org/10.1029/2005GC001045.

  13. Susceptibility of an avian pneumovirus isolated from Minnesota turkeys to physical and chemical agents.

    PubMed

    Townsend, E; Halvorson, D A; Nagaraja, K V; Shaw, D P

    2000-01-01

    Survival characteristics of a Minnesota avian pneumovirus (APV) isolated from a turkey nasoturbinate, propagated in tissue culture, and exposed to various physiochemical treatments were determined. These characteristics included survivability under various conditions. Specifically, APV was viable at temperatures of -70 C and -20 C for over 26 wk, 4 C for less than 12 wk, 20 C for less than 4 wk, 37 C for 48 hr, and 50 C for less than 6 hr. In addition, APV survived 12 freeze/thaw cycles with no loss of activity. With a variable pH for 1 hr, the titer was unaffected between the levels of pH 5 and 9. Several disinfectants, including quaternary ammonia, ethanol, iodophor, a phenol derivative, a biguanide, and bleach, were all effective in reducing the viability of the virus. After 7 days of drying at room temperature, the APV remained viable and was recovered on cell culture. PMID:10879914

  14. Substituent effect study on experimental ¹³C NMR chemical shifts of (3-(substituted phenyl)-cis-4,5-dihydroisoxazole-4,5-diyl)bis(methylene)diacetate derivatives.

    PubMed

    Kara, Yesim S

    2015-12-01

    Eleven novel (3-(substituted phenyl)-cis-4,5-dihydroisoxazole-4,5-diyl)bis(methylene) diacetate derivatives were synthesized in the present study. These dihydroisoxazole derivatives were characterized by IR, (1)H NMR, (13)C NMR and elemental analyses. Their (13)C NMR spectra were measured in Deuterochloroform (CDCl3). The correlation analysis for the substituent-induced chemical shift (SCS) with Hammett substituent constant (σ), inductive substituent constant (σI), different of resonance substituent constants (σR, σR(o)) and Swain-Lupton substituent parameters (F, R) were performed using SSP (single substituent parameter), and DSP (dual substituent parameter) methods, as well as single and multiple regression analysis. From the result of regression analysis, the effect of substituent on the (13)C NMR chemical shifts was explained. PMID:26172459

  15. Structure-based predictions of 13C-NMR chemical shifts for a series of 2-functionalized 5-(methylsulfonyl)-1-phenyl-1H-indoles derivatives using GA-based MLR method

    NASA Astrophysics Data System (ADS)

    Ghavami, Raouf; Sadeghi, Faridoon; Rasouli, Zolikha; Djannati, Farhad

    2012-12-01

    Experimental values for the 13C NMR chemical shifts (ppm, TMS = 0) at 300 K ranging from 96.28 ppm (C4' of indole derivative 17) to 159.93 ppm (C4' of indole derivative 23) relative to deuteride chloroform (CDCl3, 77.0 ppm) or dimethylsulfoxide (DMSO, 39.50 ppm) as internal reference in CDCl3 or DMSO-d6 solutions have been collected from literature for thirty 2-functionalized 5-(methylsulfonyl)-1-phenyl-1H-indole derivatives containing different substituted groups. An effective quantitative structure-property relationship (QSPR) models were built using hybrid method combining genetic algorithm (GA) based on stepwise selection multiple linear regression (SWS-MLR) as feature-selection tools and correlation models between each carbon atom of indole derivative and calculated descriptors. Each compound was depicted by molecular structural descriptors that encode constitutional, topological, geometrical, electrostatic, and quantum chemical features. The accuracy of all developed models were confirmed using different types of internal and external procedures and various statistical tests. Furthermore, the domain of applicability for each model which indicates the area of reliable predictions was defined.

  16. Influence of physico-chemical parameters of some barbituric acid derivatives on their retention on an amide embedded RP silica column.

    PubMed

    Jakab, Annamaria; Prodan, Miklos; Forgács, Esther

    2002-03-01

    Retention parameters of 45 different barbituric acid derivatives were determined on an amide embedded RP silica column (Discovery RP-AmideC16) using non-buffered water-acetonitrile eluent systems. Linear correlation were calculated between the logarithm of the capacity factor and the acetonitrile concentration in the eluent. To determine the retention behavior of barbituric acid derivatives, stepwise regression analysis (SRA) and principal component analysis (PCA) followed by two-dimensional nonlinear and modified nonlinear mapping was used. It can be concluded, the retention of barbituric acid derivatives are governed mainly by the steric parameters of the substituents. Principal component analysis indicated that the barbituric acid derivatives have mixed retention on this amide embedded RP silica column in water-acetonitrile eluent. PMID:11836055

  17. Metabolomics based on liquid chromatography with mass spectrometry reveals the chemical difference in the stems and roots derived from Ephedra sinica.

    PubMed

    Lv, Mengying; Chen, Jiaqing; Gao, Yiqiao; Sun, Jianbo; Zhang, Qianqian; Zhang, Mohan; Xu, Fengguo; Zhang, Zunjian

    2015-10-01

    To better understand different traditional uses of the stems (known as Mahuang) and roots (known as Mahuanggen) of Ephedra sinica, their chemical difference should be investigated. In this study, an ultra-fast liquid chromatography coupled with ion trap time-of-flight mass spectrometry untargeted metabolomics approach was established to reveal global chemical difference between Mahuang and Mahuanggen. Clear separation was observed in scores plots of principal component analysis and orthogonal partial least squares-discriminant analysis. Twenty two chemical markers responsible for such separation were screened out and unambiguously/tentatively characterized. Then chemical markers of pharmacologically important ephedrine and pseudoephedrine were absolutely quantified using liquid chromatography coupled with tandem mass spectrometry under multiple reaction monitoring mode. The results showed that Mahuang was rich in ephedrine-type alkaloids, while Mahuanggen was rich in macrocyclic spermine alkaloids. Additionally, different types of flavan-3-ols and flavones exist in Mahuang and Mahuanggen extracts. This research facilitates a better understanding of different traditional uses of Mahuang and Mahuanggen and provides references for chemical analysis of other medicinal plants. PMID:26224607

  18. Optical fiber chemical sensors with sol-gel derived nanomaterials for monitoring high temperature/high pressure reactions in clean energy technologies

    NASA Astrophysics Data System (ADS)

    Tao, Shiquan

    2010-04-01

    The development of sensor technologies for in situ, real time monitoring the high temperature/high pressure (HTP) chemical processes used in clean energy technologies is a tough challenge, due to the HTP, high dust and corrosive chemical environment of the reaction systems. A silica optical fiber is corrosive resistance, and can work in HTP conditions. This paper presents our effort in developing fiber optic sensors for in situ, real time monitoring the concentration of trace ammonia and hydrogen in high temperature gas samples. Preliminary test results illustrate the feasibility of using fiber optic sensor technologies for monitoring HTP processes for next generation energy industry.

  19. Plakilactones G and H from a marine sponge. Stereochemical determination of highly flexible systems by quantitative NMR-derived interproton distances combined with quantum mechanical calculations of 13C chemical shifts

    PubMed Central

    Di Micco, Simone; Zampella, Angela; D’Auria, Maria Valeria; Festa, Carmen; De Marino, Simona; Riccio, Raffaele

    2013-01-01

    Summary In this paper the stereostructural investigation of two new oxygenated polyketides, plakilactones G and H, isolated from the marine sponge Plakinastrella mamillaris collected at Fiji Islands, is reported. The stereostructural studies began on plakilactone H by applying an integrated approach of the NOE-based protocol and quantum mechanical calculations of 13C chemical shifts. In particular, plakilactone H was used as a template to extend the application of NMR-derived interproton distances to a highly flexible molecular system with simultaneous assignment of four non-contiguous stereocenters. Chemical derivatization and quantum mechanical calculations of 13C on plakilactone G along with a plausible biogenetic interconversion between plakilactone G and plakilactone H allowed us to determine the absolute configuration in this two new oxygenated polyketides. PMID:24454574

  20. Relationship between Chemical Structure and Helical Twisting Power in Optically Active Imine Dopants Derived from (R)-(+)-1-(1-Naphthyl)ethylamine

    NASA Astrophysics Data System (ADS)

    Fukuda, Kaoru; Suzuki, Hideyuki; Ni, Jin; Tokita, Masatoshi; Watanabe, Junji

    2007-08-01

    In this study, we prepared a series of imine-based chiral dopants derived from (R)-(+)-1-(1-naphthyl)ethylamine, which are soluble in liquid crystal solvent, and examined their helical twisting power (HTP) for a typical nematic host, 4'-hexyloxy-4-biphenylcarbonitrile (6-OCB). The chiral dopants basically consist of the mesogenic aromatic part, which is directly bound to the chiral naphthylethyl part by imine linkage, and the alkyl tail part. These mono-imine derivatives have the following features. (1) The extension of the aromatic part drastically increases the HTP and (2) the attachment of the alkoxy tail part is also effective as HTP inducers, indicating the importance of structural similarity between the liquid crystal host molecule and the chiral dopant. HTPs were also examined for di-imine derivatives with two chiral parts at both edges of the mesogenic part. In this case, HTPs are variable from 65 to 140 μm-1, depending on the conformation of the central mesogenic group that produces the delicate coordination of the two chiral parts. The maximum value of 140 μm-1 may be one of the largest values among the chiral dopants that have thus far been prepared on a basis of the asymmetric carbon. By mixing a low percentage of this dopant, the resulting chiral nematic liquid crystals can possess pitches comparable to the wavelength of visible light.

  1. Optical poling effect and optical absorption of cyan, ethylcarboxyl and tert -buthyl derivatives of 1H-pyrazolo[3,4-b]quinoline: experiment and quantum-chemical simulations

    NASA Astrophysics Data System (ADS)

    Ko?cie?, E.; Sanetra, J.; Gondek, E.; Jarosz, B.; Kityk, I. V.; Ebothe, J.; Kityk, A. V.

    2005-06-01

    We present here results of experimental studies and quantum-chemical simulations of optical absorption and optical poling effects performed on a new synthesized cyan, ethylcarboxyl and tert -buthyl derivatives of 1H-pyrazolo[3,4-b]quinoline incorporated into polymer matrix or dissolved in organic solutions. The efficiency of second-order optical susceptibility d vs photoinduced power density I clearly saturates to certain magnitude d at sufficient power densities ( I? 1.3 GW cm -2). Comparing experimental data and results of semiempirical quantum-chemical simulations one can conclude that there exists generally a good correlation between the magnitude of saturated susceptibilities d and macroscopic hyperpolarizabilities for all compounds except the chromophore 1,3-dimethyl-6-cyano-[PQ] only. The discrepancy for this compound may reflect a specific contribution of surrounding polymer matrix. According to the quantum chemical analysis the methyl-containing cyan and ethylocarcoxyl derivatives reveal four/five strong absorption bands in the spectral range 200-500 nm. A substitution of the methyl groups by the phenyl group causes the substantial changes of the absorption spectra mainly in the spectral range 240-370 nm. Measured and calculated absorption spectra manifest rather good agreement mainly in the part regarding the spectral positions of the first oscillator (absorption threshold). The quantum-chemical PM3 method shows the best agreement with experiment. At the same time a considerable broadening almost of all absorption bands appears as a characteristic feature of all measured spectra. The discrepancies between the calculated and the measured spectra are attributed to electron-vibronic coupling as well as to a specific rotational dynamics of phenyl rings.

  2. Some Phthalocyanine and Naphthalocyanine Derivatives as Corrosion Inhibitors for Aluminium in Acidic Medium: Experimental, Quantum Chemical Calculations, QSAR Studies and Synergistic Effect of Iodide Ions.

    PubMed

    Dibetsoe, Masego; Olasunkanmi, Lukman O; Fayemi, Omolola E; Yesudass, Sasikumar; Ramaganthan, Baskar; Bahadur, Indra; Adekunle, Abolanle S; Kabanda, Mwadham M; Ebenso, Eno E

    2015-01-01

    The effects of seven macrocyclic compounds comprising four phthalocyanines (Pcs) namely 1,4,8,11,15,18,22,25-octabutoxy-29H,31H-phthalocyanine (Pc1), 2,3,9,10,16,17,23,24-octakis(octyloxy)-29H,31H-phthalocyanine (Pc2), 2,9,16,23-tetra-tert-butyl-29H,31H-phthalocyanine (Pc3) and 29H,31H-phthalocyanine (Pc4), and three naphthalocyanines namely 5,9,14,18,23,27,32,36-octabutoxy-2,3-naphthalocyanine (nPc1), 2,11,20,29-tetra-tert-butyl-2,3-naphthalocyanine (nPc2) and 2,3-naphthalocyanine (nP3) were investigated on the corrosion of aluminium (Al) in 1 M HCl using a gravimetric method, potentiodynamic polarization technique, quantum chemical calculations and quantitative structure activity relationship (QSAR). Synergistic effects of KI on the corrosion inhibition properties of the compounds were also investigated. All the studied compounds showed appreciable inhibition efficiencies, which decrease with increasing temperature from 30 °C to 70 °C. At each concentration of the inhibitor, addition of 0.1% KI increased the inhibition efficiency compared to the absence of KI indicating the occurrence of synergistic interactions between the studied molecules and I(-) ions. From the potentiodynamic polarization studies, the studied Pcs and nPcs are mixed type corrosion inhibitors both without and with addition of KI. The adsorption of the studied molecules on Al surface obeys the Langmuir adsorption isotherm, while the thermodynamic and kinetic parameters revealed that the adsorption of the studied compounds on Al surface is spontaneous and involves competitive physisorption and chemisorption mechanisms. The experimental results revealed the aggregated interactions between the inhibitor molecules and the results further indicated that the peripheral groups on the compounds affect these interactions. The calculated quantum chemical parameters and the QSAR results revealed the possibility of strong interactions between the studied inhibitors and metal surface. QSAR analysis on the quantum chemical parameters obtained with B3LYP/6-31G (d,p) method show that a combination of two quantum chemical parameters to form a composite index provides the best correlation with the experimental data. PMID:26343626

  3. A three-dimensional chemical phase pharmacophore mapping, QSAR modelling and electronic feature analysis of benzofuran salicylic acid derivatives as LYP inhibitors.

    PubMed

    Suryanarayanan, V; Singh, S Kumar; Tripathi, S Kumar; Selvaraj, C; Reddy, K Konda; Karthiga, A

    2013-01-01

    Lymphoid tyrosine phosphatase (LYP), encoded by the PTPN22 gene, has a critical negative regulatory role in T-cell antigen receptor (TCR) and emerged as a promising drug target for human autoimmune diseases. A five-point pharmacophore with two hydrogen bond acceptors, one hydrogen bond donor and two aromatic ring features was generated for a series of benzofuran salicylic acid derivatives as LYP inhibitors in order to elucidate their anti-autoimmune activity. The generated pharmacophore yielded a significant 3D-QSAR model with r(2) of 0.9146 for a training set of 27 compounds. The model also showed excellent predictive power with Q(2) of 0.7068 for a test set of eight compounds. The investigation of the 3D-QSAR model has revealed the structural insights which could lead to more potent analogues. The most active and inactive compounds were further subjected to electronic structure analysis using density functional theory (DFT) at B3LYP/3-21(?)G level to support the 3D-QSAR predictions. The results obtained from this study are expected to be useful in the proficient design and development of benzofuran salicylic acid derivatives as inhibitors of LYP. PMID:23987088

  4. Identification of UV-protective Activators of Nuclear Factor Erythroid-derived 2-Related Factor 2 (Nrf2) by Combining a Chemical Library Screen with Computer-based Virtual Screening*

    PubMed Central

    Lieder, Franziska; Reisen, Felix; Geppert, Tim; Sollberger, Gabriel; Beer, Hans-Dietmar; auf dem Keller, Ulrich; Schäfer, Matthias; Detmar, Michael; Schneider, Gisbert; Werner, Sabine

    2012-01-01

    Nuclear factor erythroid-derived 2-related factor 2 (Nrf2) is a master regulator of cellular antioxidant defense systems, and activation of this transcription factor is a promising strategy for protection of skin and other organs from environmental insults. To identify efficient Nrf2 activators in keratinocytes, we combined a chemical library screen with computer-based virtual screening. Among 14 novel Nrf2 activators, the most potent compound, a nitrophenyl derivative of 2-chloro-5-nitro-N-phenyl-benzamide, was characterized with regard to its molecular mechanism of action. This compound induced the expression of cytoprotective genes in keratinocytes isolated from wild-type but not from Nrf2-deficient mice. Most importantly, it showed low toxicity and protected primary human keratinocytes from UVB-induced cell death. Therefore, it represents a potential lead compound for the development of drugs for skin protection under stress conditions. Our study demonstrates that chemical library screening combined with advanced computational similarity searching is a powerful strategy for identification of bioactive compounds, and it points toward an innovative therapeutic approach against UVB-induced skin damage. PMID:22851183

  5. Analysis of Phenacylester Derivatives of Fatty Acids from Human Skin Surface Sebum by Reversed-Phase HPLC: Chromatographic Mobility as a Function of Physico-Chemical Properties

    PubMed Central

    Bodoprost, Juliana; Rosemeyer, Helmut

    2007-01-01

    A set of 13 fatty acids was transformed into their phenacyl esters by reaction with phenacyl bromide in acetonitrile using 18-crown-6 as phase-transfer catalyst. Conditions for the RP-18 HPL chromatographic separation of most of the esters has been worked out. Using this standard the fatty acid spectra from skin surface sebum lipids of 17 test persons was taken after microwave-assisted hydrolysis, neutralization and extraction with n-hexane. Quantitative evaluation of the chromatograms exhibits that oleic acid predominates in the sebum of all test persons. In the second part of the work the chromatographic mobility (RE values) of fatty acid phenacyl esters is correlated with calculated physico-chemical parameters of the corresponding acids. The best linear correlation was found between the RE and the logP values. This is helpful for the structural elucidation of un-identified fatty acids in a chromatogram.

  6. Physico-chemical characterization of SOA derived from catechol and guaiacol - a model substance for the aromatic fraction of atmospheric HULIS

    NASA Astrophysics Data System (ADS)

    Ofner, J.; Krüger, H.-U.; Grothe, H.; Schmitt-Kopplin, P.; Whitmore, K.; Zetzsch, C.

    2011-01-01

    Secondary organic aerosol (SOA) was produced from the aromatic precursors catechol and guaiacol by reaction with ozone in the presence and absence of simulated sunlight and humidity and investigated for its properties as a proxy for HUmic-LIke Substances (HULIS). Beside a small particle size, a relatively low molecular weight and typical optical features in the UV/VIS spectral range, HULIS contain a typical aromatic and/or olefinic chemical structure and highly oxidized functional groups within a high chemical diversity. Various methods were used to characterize the secondary organic aerosols obtained: Fourier transform infrared spectroscopy (FTIR) demonstrated the formation of several carbonyl containing functional groups as well as structural and functional differences between aerosols formed at different environmental conditions. UV/VIS spectroscopy of filter samples showed that the particulate matter absorbs far into the visible range up to more than 500 nm. Ultrahigh resolved mass spectroscopy (ICR-FT/MS) determined O/C-ratios between 0.3 and 1 and observed m/z ratios between 200 and 450 to be most abundant. Temperature-programmed-pyrolysis mass spectroscopy (TPP-MS) identified carboxylic acids and lactones/esters as major functional groups. Particle sizing using a condensation-nucleus-counter and differential-mobility-particle-sizer (CNC/DMPS) monitored the formation of small particles during the SOA formation process. Particle imaging, using field-emission-gun scanning electron microscopy (FEG-SEM), showed spherical particles, forming clusters and chains. We conclude that catechol and guaiacol are appropriate precursors for studies of the processing of aromatic SOA with atmospheric HULIS properties on the laboratory scale.

  7. Hydroxamic acids derived from 2-hydroxy-2H-1,4-benzoxazin-3(4H)-one: key defense chemicals of cereals.

    PubMed

    Niemeyer, Hermann M

    2009-03-11

    Many cereals accumulate hydroxamic acids derived from 2-hydroxy-2H-1,4-benzoxazin-3(4H)-one. These benzoxazinoid hydroxamic acids are involved in defense of maize against various lepidopteran pests, most notably the European corn borer, in defense of cereals against various aphid species, and in allelopathy affecting the growth of weeds associated with rye and wheat crops. The role of benzoxazinoid hydroxamic acids in defense against fungal infection is less clear and seems to depend on the nature of the interactions at the plant-fungus interface. Efficient use of benzoxazinoid hydroxamic acids as resistance factors has been limited by the inability to selectively increase their levels at the plant growth stage and the plant tissues where they are mostly needed for a given pest. Although the biosynthesis of benzoxazinoid hydroxamic acids has been elucidated, the genes and mechanisms controlling their differential expression in different plant tissues and along plant ontogeny remain to be unraveled. PMID:19199602

  8. 1H NMR chemical shift studies of pregn-5-ene-3β,20( R)-diol and pregn-5-ene-3β-ol,20-one D-glucopyranoside derivatives

    NASA Astrophysics Data System (ADS)

    Warthen, J. D.; Waters, R. M.; Oliver, J. E.

    The 1H NMR chemical shift and J value data of a series of pregn-5-ene-3β,20( R)-diol/pregn-5-ene-3β-ol, 20-one D-glucopyranosides and D-glucopyranoside derivatives are reported because of their relevance to the structure determination of pregnenediol tri- and diglucosides on tobacco hornworm eggs. Effects of various substituents at the 3β- and 20( R)-positions of the pregn-5-ene nucleus upon chemical shifts of selected protons on the pregn-5-ene nucleus are discussed. Chemical shifts of selected protons on the D-glucopyranoside nucleus/nuclei are also discussed. Differentiation between the pregn-5-ene substitution points, between anomeric glucose configurations and between anomeric protons on β- D-glucosides at 3β and 20( R) is demonstrated. A COSY NMR analysis of the Manduca peracetylated triglucoside is utilized to show the interaction of the three anomeric β- D-glucoside protons and to distinguish the dissimilar one.

  9. Saturated amine oxides: Part 8. Hydroacridines: Part 27. Effects of N-oxidation and of N-quaternization on the 15N NMR chemical shifts of N-methylpiperidine-derived mono-, bi-, and tricycloaliphatic tertiary amines.

    PubMed

    Potmischil, Francisc; Duddeck, Helmut; Nicolescu, Alina; Deleanu, Calin

    2007-03-01

    The (15)N chemical shifts of 13 N-methylpiperidine-derived mono-, bi- and tricycloaliphatic tertiary amines, their methiodides and their N-epimeric pairs of N-oxides were measured, and the contributions of specific structural parameters to the chemical shifts were determined by multilinear regression analysis. Within the examined compounds, the effects of N-oxidation upon the (15)N chemical shifts of the amines vary from +56 ppm to +90 ppm (deshielding), of which approx. +67.7 ppm is due to the inductive effect of the incoming N(+)--O(-) oxygen atom, whereas the rest is due to the additive shift effects of the various C-alkyl substituents of the piperidine ring. The effects of quaternization vary from -3.1 ppm to +29.3 ppm, of which approx. +8.9 ppm is due to the inductive effect of the incoming N(+)--CH(3) methyl group, and the rest is due to the additive shift effects of the various C-alkyl substituents of the piperidine ring. The shift effects of the C-alkyl substituents in the amines, the N-oxides and the methiodides are discussed. PMID:17221923

  10. Mammalian and teleost cell line bioassay and chemically derived 2,3,7,8-tetrachlorodibenzo-p-dioxin equivalent concentrations in lake trout (Salvelinus namaycush) from Lake Superior and Lake Ontario, North America

    SciTech Connect

    Whyte, J.J.; Heuvel, M.R. van den; Clemons, J.H.; Dixon, D.G.; Bols, N.C.; Huestis, S.Y.; Servos, M.R.

    1998-11-01

    For livers of lake trout from three Great Lakes sites, the 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) equivalent concentrations (TEQs) were determined in four ways. Bioassay-derived (BD) TEQs were measured with rat (H4IIE) and rainbow trout (RTL-W1) cell lines, and chemistry-derived (CD) TEQs were calculated with TCDD equivalency factors (TEFs) derived with H4IIE and RTL-W1. Generally, BD-TEQs and CD-TEQs for individual samples did not differ significantly for either H4IIE or RTL-W1, indicating that all of the AhR-active compounds in a sample were accounted for by the congener analysis and that these compounds acted in an additive fashion in both mammalian and piscine systems. However, contributions of individual chemicals to overall CD-TEQs differed with H4IIE and RTL-W1 TEFs, and for some individual samples. TEQs did depend on the method used. Hepatic TEQs and ethoxyresorufin-O-deethylase (EROD) levels differed significantly between sites. For TEQs, the order was Glenora > Jackfish Bay > Black Bay; for EROD activity, the order was Jackfish Bay > Glenora = Black Bay. No correlation was found between hepatic TEQs and EROD activity, which suggests that the two measurements are evaluating different but related consequences of contaminant exposure.

  11. Chemical Composition and Biological Activity of Extracts Obtained by Supercritical Extraction and Ethanolic Extraction of Brown, Green and Red Propolis Derived from Different Geographic Regions in Brazil

    PubMed Central

    Machado, Bruna Aparecida Souza; Silva, Rejane Pina Dantas; Barreto, Gabriele de Abreu; Costa, Samantha Serra; da Silva, Danielle Figuerêdo; Brandão, Hugo Neves; da Rocha, José Luiz Carneiro; Dellagostin, Odir Antônio; Henriques, João Antônio Pegas; Umsza-Guez, Marcelo Andres; Padilha, Francine Ferreira

    2016-01-01

    The variations in the chemical composition, and consequently, on the biological activity of the propolis, are associated with its type and geographic origin. Considering this fact, this study evaluated propolis extracts obtained by supercritical extraction (SCO2) and ethanolic extraction (EtOH), in eight samples of different types of propolis (red, green and brown), collected from different regions in Brazil. The content of phenolic compounds, flavonoids, in vitro antioxidant activity (DPPH and ABTS), Artepillin C, p-coumaric acid and antimicrobial activity against two bacteria were determined for all extracts. For the EtOH extracts, the anti-proliferative activity regarding the cell lines of B16F10, were also evaluated. Amongst the samples evaluated, the red propolis from the Brazilian Northeast (states of Sergipe and Alagoas) showed the higher biological potential, as well as the larger content of antioxidant compounds. The best results were shown for the extracts obtained through the conventional extraction method (EtOH). However, the highest concentrations of Artepillin C and p-coumaric acid were identified in the extracts from SCO2, indicating a higher selectivity for the extraction of these compounds. It was verified that the composition and biological activity of the Brazilian propolis vary significantly, depending on the type of sample and geographical area of collection. PMID:26745799

  12. Chemical Composition and Biological Activity of Extracts Obtained by Supercritical Extraction and Ethanolic Extraction of Brown, Green and Red Propolis Derived from Different Geographic Regions in Brazil.

    PubMed

    Machado, Bruna Aparecida Souza; Silva, Rejane Pina Dantas; Barreto, Gabriele de Abreu; Costa, Samantha Serra; Silva, Danielle Figuerêdo da; Brandão, Hugo Neves; Rocha, José Luiz Carneiro da; Dellagostin, Odir Antônio; Henriques, João Antônio Pegas; Umsza-Guez, Marcelo Andres; Padilha, Francine Ferreira

    2016-01-01

    The variations in the chemical composition, and consequently, on the biological activity of the propolis, are associated with its type and geographic origin. Considering this fact, this study evaluated propolis extracts obtained by supercritical extraction (SCO2) and ethanolic extraction (EtOH), in eight samples of different types of propolis (red, green and brown), collected from different regions in Brazil. The content of phenolic compounds, flavonoids, in vitro antioxidant activity (DPPH and ABTS), Artepillin C, p-coumaric acid and antimicrobial activity against two bacteria were determined for all extracts. For the EtOH extracts, the anti-proliferative activity regarding the cell lines of B16F10, were also evaluated. Amongst the samples evaluated, the red propolis from the Brazilian Northeast (states of Sergipe and Alagoas) showed the higher biological potential, as well as the larger content of antioxidant compounds. The best results were shown for the extracts obtained through the conventional extraction method (EtOH). However, the highest concentrations of Artepillin C and p-coumaric acid were identified in the extracts from SCO2, indicating a higher selectivity for the extraction of these compounds. It was verified that the composition and biological activity of the Brazilian propolis vary significantly, depending on the type of sample and geographical area of collection. PMID:26745799

  13. Can Small Chemical Modifications of Natural Pan-inhibitors Modulate the Biological Selectivity? The Case of Curcumin Prenylated Derivatives Acting as HDAC or mPGES-1 Inhibitors.

    PubMed

    Iranshahi, Mehrdad; Chini, Maria Giovanna; Masullo, Milena; Sahebkar, Amirhossein; Javidnia, Azita; Chitsazian Yazdi, Mahsa; Pergola, Carlo; Koeberle, Andreas; Werz, Oliver; Pizza, Cosimo; Terracciano, Stefania; Piacente, Sonia; Bifulco, Giuseppe

    2015-12-24

    Curcumin, or diferuloylmethane, a polyphenolic molecule isolated from the rhizome of Curcuma longa, is reported to modulate multiple molecular targets involved in cancer and inflammatory processes. On the basis of its pan-inhibitory characteristics, here we show that simple chemical modifications of the curcumin scaffold can regulate its biological selectivity. In particular, the curcumin scaffold was modified with three types of substituents at positions C-1, C-8, and/or C-8' [C5 (isopentenyl, 5-8), C10 (geranyl, 9-12), and C15 (farnesyl, 13, 14)] in order to make these molecules more selective than the parent compound toward two specific targets: histone deacetylase (HDAC) and microsomal prostaglandin E2 synthase-1 (mPGES-1). From combined in silico and in vitro analyses, three selective inhibitors by proper substitution at position 8 were revealed. Compound 13 has improved HDAC inhibitory activity and selectivity with respect to the parent compound, while 5 and 9 block the mPGES-1 enzyme. We hypothesize about the covalent interaction of curcumin, 5, and 9 with the mPGES-1 binding site. PMID:26588603

  14. Assessment and Applications of NASA Ozone Data Products Derived from Aura OMI-MLS Satellite Measurements in Context of the GMI Chemical Transport Model

    NASA Technical Reports Server (NTRS)

    Ziemke, J. R.; Olsen, M. A.; Witte, J. C.; Douglass, A. R.; Strahan, S. E.; Wargan, K.; Liu, X.; Schoeberl, M. R.; Yang, K.; Kaplan, T. B.; Pawson, S.; Duncan, B. N.; Newman, P. A.; Bhartia, K.; Heney, M. K.

    2013-01-01

    Measurements from the Ozone Monitoring Instrument (OMI) and Microwave Limb Sounder (MLS), both onboard the Aura spacecraft, have been used to produce daily global maps of column and profile ozone since August 2004. Here we compare and evaluate three strategies to obtain daily maps of tropospheric and stratospheric ozone from OMI and MLS measurements: trajectory mapping, direct profile retrieval, and data assimilation. Evaluation is based upon an assessment that includes validation using ozonesondes and comparisons with the Global Modeling Initiative (GMI) chemical transport model (CTM). We investigate applications of the three ozone data products from near-decadal and inter-annual timescales to day-to-day case studies. Zonally averaged inter-annual changes in tropospheric ozone from all of the products in any latitude range are of the order 1-2 Dobson Units while changes (increases) over the 8-year Aura record investigated http://eospso.gsfc.nasa.gov/atbd-category/49 vary approximately 2-4 Dobson Units. It is demonstrated that all of the ozone products can measure and monitor exceptional tropospheric ozone events including major forest fire and pollution transport events. Stratospheric ozone during the Aura record has several anomalous inter-annual events including stratospheric warming split events in the Northern Hemisphere extra-tropics that are well captured using the data assimilation ozone profile product. Data assimilation with continuous daily global coverage and vertical ozone profile information is the best of the three strategies at generating a global tropospheric and stratospheric ozone product for science applications.

  15. Assessment and Applications of NASA Ozone Data Products Derived from Aura OMI/MLS Satellite Measurements in Context of the GMI Chemical Transport Model

    NASA Astrophysics Data System (ADS)

    Ziemke, J. R.; Olsen, M. A.; Witte, J. C.; Douglass, A. R.

    2014-12-01

    Measurements from the Ozone Monitoring Instrument (OMI) and Microwave Limb Sounder (MLS), both onboard the Aura spacecraft, have been used to produce daily global maps of column and profile ozone since August 2004. Here we compare and evaluate three strategies to obtain daily maps of tropospheric and stratospheric ozone from OMI and MLS measurements: trajectory mapping, direct profile retrieval, and data assimilation. Evaluation is based on an assessment that includes validation using ozonesondes and comparisons with the Global Modeling Initiative (GMI) chemical transport model (CTM). We investigate applications of the three ozone data products from near-decadal and inter-annual timescales to day-to-day case studies. Inter-annual changes in zonal mean tropospheric ozone from all of the products in any latitude range are of the order 1-2 Dobson Units while changes (increases) over the 8-year Aura record investigated vary by 2-4 Dobson Units. It is demonstrated that all of the ozone products can measure and monitor exceptional tropospheric ozone events including major forest fire and pollution transport events. Stratospheric ozone during the Aura record has several anomalous inter-annual events including split stratospheric warmings in the Northern Hemisphere extra-tropics that are well captured using the data assimilation ozone profile product. Data assimilation with continuous daily global coverage and vertical ozone profile information is the best of the three strategies at generating a global tropospheric and stratospheric ozone product for science applications.

  16. Derivatives of 3:4-xylidine and related compounds as inhibitors of influenza virus: relationships between chemical structure and biological activity

    PubMed Central

    Clark, R. J.; Isaacs, A.; Walker, J.

    1958-01-01

    A series of compounds, based primarily on 3:4-xylidine, was examined for inhibitory activity towards the growth of influenza virus in tissue culture. Marked dependence of inhibitory activity upon chemical structure was observed particularly when the 3:4-xylyl group was replaced by other simple aryl radicals. N-(2-Piperidinoethyl)-3:4-xylidine dihydrochloride, a typical compound combining high intrinsic inhibitory activity with no obvious toxicity towards the host tissues, did not inactivate the virus directly before its adsorption, did not interfere with adsorption of virus by the tissues, and did not inhibit the release of freshly synthesized virus by the tissues, but specifically depressed the synthesis of viral haemagglutinin to a greater extent than it depressed the synthesis of complement-fixing soluble antigen. The inhibition of growth of influenza virus caused by this compound in tissue culture was reversed by appropriate addition of 4:5-dimethyl-o-phenylenediamine, but not apparently by riboflavin or by vitamin B12. The action of this substance, and, by inference, of related compounds, in inhibiting viral synthesis may be the result of depressed cytoplasmic protein synthesis. PMID:13618548

  17. An Intercomparison and Evaluation of Aircraft-Derived and Simulated CO from Seven Chemical Transport Models During the TRACE-P Experiment

    NASA Technical Reports Server (NTRS)

    Kiley, C. M.; Fuelberg, Henry E.; Palmer, P. I.; Allen, D. J.; Carmichael, G. R.; Jacob, D. J.; Mari, C.; Pierce, R. B.; Pickering, K. E.; Tang, Y.

    2002-01-01

    Four global scale and three regional scale chemical transport models are intercompared and evaluated during NASA's TRACE-P experiment. Model simulated and measured CO are statistically analyzed along aircraft flight tracks. Results for the combination of eleven flights show an overall negative bias in simulated CO. Biases are most pronounced during large CO events. Statistical agreements vary greatly among the individual flights. Those flights with the greatest range of CO values tend to be the worst simulated. However, for each given flight, the models generally provide similar relative results. The models exhibit difficulties simulating intense CO plumes. CO error is found to be greatest in the lower troposphere. Convective mass flux is shown to be very important, particularly near emissions source regions. Occasionally meteorological lift associated with excessive model-calculated mass fluxes leads to an overestimation of mid- and upper- tropospheric mixing ratios. Planetary Boundary Layer (PBL) depth is found to play an important role in simulating intense CO plumes. PBL depth is shown to cap plumes, confining heavy pollution to the very lowest levels.

  18. Chemical composition and larvicidal activity of edible plant-derived essential oils against the pyrethroid-susceptible and -resistant strains of Aedes aegypti (Diptera: Culicidae).

    PubMed

    Sutthanont, Nataya; Choochote, Wej; Tuetun, Benjawan; Junkum, Anuluck; Jitpakdi, Atchariya; Chaithong, Udom; Riyong, Doungrat; Pitasawat, Benjawan

    2010-06-01

    The chemical compositions and larvicidal potential against mosquito vectors of selected essential oils obtained from five edible plants were investigated in this study. Using a GC/MS, 24, 17, 20, 21, and 12 compounds were determined from essential oils of Citrus hystrix, Citrus reticulata, Zingiber zerumbet, Kaempferia galanga, and Syzygium aromaticum, respectively. The principal constituents found in peel oil of C. hystrix were beta-pinene (22.54%) and d-limonene (22.03%), followed by terpinene-4-ol (17.37%). Compounds in C. reticulata peel oil consisted mostly of d-limonene (62.39%) and gamma-terpinene (14.06%). The oils obtained from Z. zerumbet rhizome had alpha-humulene (31.93%) and zerumbone (31.67%) as major components. The most abundant compounds in K. galanga rhizome oil were 2-propeonic acid (35.54%), pentadecane (26.08%), and ethyl-p-methoxycinnamate (25.96%). The main component of S. aromaticum bud oil was eugenol (77.37%), with minor amounts of trans-caryophyllene (13.66%). Assessment of larvicidal efficacy demonstrated that all essential oils were toxic against both pyrethroid-susceptible and resistant Ae. aegypti laboratory strains at LC50, LC95, and LC99 levels. In conclusion, we have documented the promising larvicidal potential of essential oils from edible herbs, which could be considered as a potentially alternative source for developing novel larvicides to be used in controlling vectors of mosquito-borne disease. PMID:20618656

  19. HPLC analysis of tetrahydrobiopterin and its pteridine derivatives using sequential electrochemical and fluorimetric detection: application to tetrahydrobiopterin autoxidation and chemical oxidation

    PubMed Central

    Biondi, Roberto; Ambrosio, Giuseppe; De Pascali, Francesco; Tritto, Isabella; Capodicasa, Enrico; Druhan, Lawrence J.; Hemann, Craig; Zweier, Jay L.

    2012-01-01

    Tetrahydrobiopterin (BH4) is an essential cofactor of endothelial nitric oxide (NO) synthase and when depleted, endothelial dysfunction results with decreased production of NO. BH4 is also an anti-oxidant being a good “scavenger” of oxidative species. NADPH oxidase, xanthine oxidase, and mitochondrial enzymes producing reactive oxygen species (ROS) can induce elevated oxidant stress and cause BH4 oxidation and subsequent decrease in NO production and bioavailability. In order to define the process of ROS-mediated BH4 degradation, a sensitive method for monitoring pteridine redox-state changes is required. Considering that the conventional fluorescence method is an indirect method requiring conversion of all pteridines to oxidized forms, it would be beneficial to use a rapid quantitative assay for the individual detection of BH4 and its related pteridine metabolites. To study, in detail, the BH4 oxidative pathways, a rapid direct sensitive HPLC assay of BH4 and its pteridine derivatives was adapted using sequential electrochemical and fluorimetric detection. We examined BH4 autoxidation, hydrogen peroxide- and superoxide-driven oxidation, and Fenton reaction hydroxyl radical-driven BH4 transformation. We demonstrate that the formation of the primary two-electron oxidation product, dihydrobiopterin (BH2), predominates with oxygen-induced BH4 autoxidation and superoxide-catalyzed oxidation, while the irreversible metabolites, pterin and dihydroxanthopterin (XH2), are largely produced during hydroxyl radical-driven BH4 oxidation. PMID:22286026

  20. Part I. Naltrexone-derived conjugate addition ligands for opioid receptors. Part II. Chemical and enantioselective aspects of the metabolism of verapamil

    SciTech Connect

    Olsen, L.D.

    1987-01-01

    Selective chemoaffinity ligands to aid in identification and purification of opioid receptor subtypes were prepared from 6..cap alpha..- and 6..beta..-naltrexol, obtained stereoselectively from the ..mu..-receptor antagonist naltrexone. The targets were the 6..cap alpha..- and 6..beta..-methacrylate ethers and 6..cap alpha..- and 6..beta..-methacrylate esters prepared from reaction of 6..cap alpha..- and 6..beta..-naltrexol with methyl ..cap alpha..-(bromomethyl)acrylate or methacryloyl chloride. Of three methacrylate derivatives, the 6..cap alpha..-ether was the most potent in an opioid receptor binding assay with (/sup 3/H)-naltrexone. In the presence of sodium ion, preincubation of the 6..cap alpha..-ether resulted in recovery of about 60% of original (/sup 3/H)-naltrexone binding suggesting some irreversible effects. The methacrylate esters precipitated withdrawal in morphine dependent monkeys. The enantiomers of verapamil, a calcium channel antagonist, have different pharmacological and pharmacokinetic properties. The oxidative metabolism of verapamil was studied in rat and human liver microsomes and in man after a single oral dose.

  1. Bone marrow-derived mesenchymal stem cell transplantation ameliorates oxidative stress and restores intestinal mucosal permeability in chemically induced colitis in mice

    PubMed Central

    Sun, Tao; Gao, Guang-Zhou; Li, Rong-Fu; Li, Xin; Li, Da-Wei; Wu, Shan-Shan; Yeo, Anthony ET; Jin, Bo

    2015-01-01

    Background: Ulcerative colitis (UC) can be viewed as an autoimmune disease. Bone marrow-derived mesenchymal stem cells (MSCs) with its regenerative, cellular multi-lineage and immunomodulatory abilities can influence the repair of damaged tissues in UC. This study investigated the effects of MSCs transplantation on the mice intestinal barrier in response to oxidative stress injury. Methods: Colitis was induced by daily consecutive administration of 5% dextran sulfate sodium (DSS) solution for 7 days. Male murine MSCs were isolated and transplanted into female mice via injection in the tail vein. Serum and colon specimens were collected at 12 h, 24 h, 3 d, 7 d and 14 d after injection. Serum levels of D-lactate (D-LAC), diamine oxidase (DAO), colonic levels of malondialdehyde (MDA) and superoxide dismutase (SOD) were quantified. The SRY protein of the male sex determinant gene expression and E-cadherin were also ascertained intracellularly. Results: Three days after receiving male MSCs transplantation, SRY protein expression was detected. The quantity increased on successive days. Serum levels of D-LAC and DAO, colonic MDA and SOD normalized in a shorter time period compared to controls (p<0.05). Not surprisingly, histological regeneration of tissue and E-cadherin expression in the colon of MSCs transplanted mice also occurred in a shorter time period than controls. Conclusions: Transplanted MSCs restored mucosal permeability, and minimized oxidative stress related injury. PMID:26175850

  2. Growth of ferroelectric Ba0.8Sr0.2TiO3 epitaxial films by ultraviolet pulsed laser irradiation of chemical solution derived precursor layers

    NASA Astrophysics Data System (ADS)

    Queraltó, A.; Pérez del Pino, A.; de la Mata, M.; Arbiol, J.; Tristany, M.; Gómez, A.; Obradors, X.; Puig, T.

    2015-06-01

    Highly crystalline epitaxial Ba0.8Sr0.2TiO3 (BST) thin-films are grown on (001)-oriented LaNiO3-buffered LaAlO3 substrates by pulsed laser irradiation of solution derived barium-zirconium-titanium precursor layers using a UV Nd:YAG laser source at atmospheric conditions. The structural analyses of the obtained films, studied by X-ray diffractometry and transmission electron microscopy, demonstrate that laser processing allows the growth of tens of nm-thick BST epitaxial films with crystalline structure similar to that of films obtained through conventional thermal annealing methods. However, the fast pulsed nature of the laser employed leads to crystallization kinetic evolution orders of magnitude faster than in thermal treatments. The combination of specific photothermal and photochemical mechanisms is the main responsible for the ultrafast epitaxial laser-induced crystallization. Piezoresponse microscopy measurements demonstrate equivalent ferroelectric behavior in laser and thermally annealed films, being the piezoelectric constant ˜25 pm V-1.

  3. Synthesis, antimicrobial evaluation and theoretical prediction of NMR chemical shifts of thiazole and selenazole derivatives with high antifungal activity against Candida spp.

    NASA Astrophysics Data System (ADS)

    Łączkowski, Krzysztof Z.; Motylewska, Katarzyna; Baranowska-Łączkowska, Angelika; Biernasiuk, Anna; Misiura, Konrad; Malm, Anna; Fernández, Berta

    2016-03-01

    Synthesis and investigation of antimicrobial activities of novel thiazoles and selenazoles is presented. Their structures were determined using NMR, FAB(+)-MS, HRMS and elemental analyses. To support the experiment, theoretical calculations of the 1H NMR shifts were carried out for representative systems within the DFT B3LYP/6-311++G** approximation which additionally confirmed the structure of investigated compounds. Among the derivatives, compounds 4b, 4h, 4j and 4l had very strong activity against reference strains of Candida albicans ATCC and Candida parapsilosis ATCC 22019 with MIC = 0.49-7.81 μg/ml. In the case of compounds 4b, 4c, 4h - 4j and 4l, the activity was very strong against of Candida spp. isolated from clinical materials, i.e. C. albicans, Candida krusei, Candida inconspicua, Candida famata, Candida lusitaniae, Candida sake, C. parapsilosis and Candida dubliniensis with MIC = 0.24-15.62 μg/ml. The activity of several of these was similar to the activity of commonly used antifungal agent fluconazole. Additionally, compounds 4m - 4s were found to be active against Gram-positive bacteria, both pathogenic staphylococci Staphylococcus aureus ATCC with MIC = 31.25-125 μg/ml and opportunistic bacteria, such as Staphylococcus epidermidis ATCC 12228 and Micrococcus luteus ATCC 10240 with MIC = 7.81-31.25 μg/ml.

  4. Electrochemical and chemical oxidation of [Pt2(mu-pyrophosphite)4]4- revisited: characterization of a nitrosyl derivative, [Pt2(mu-pyrophosphite)4(NO)]3-.

    PubMed

    Bennett, Martin A; Bhargava, Suresh K; Bond, Alan M; Bansal, Vipul; Forsyth, Craig M; Guo, Si-Xuan; Privér, Steven H

    2009-03-16

    Electrochemical studies of the salts [cat](4)[Pt(2)(mu-pop)(4)] (cat(+) = Bu(4)N(+) or PPN(+) [Ph(3)P=N=PPh(3)](+); pop = pyrophosphite, [P(2)O(5)H(2)](2-)) have been carried out in dichloromethane. In agreement with published studies of K(4)[Pt(2)(mu-pop)(4)] in water and [Ph(4)As](4)[Pt(2)(mu-pop)(4)] in acetonitrile, the [Pt(2)(mu-pop)(4)](4-) anion is found to undergo an initial one-electron oxidation under conditions of cyclic voltammetry to a short-lived trianion, [Pt(2)(mu-pop)(4)](3-). However, in the more weakly coordinating solvent dichloromethane, [Pt(2)(mu-pop)(4)](3-) appears to undergo oligomerization instead of solvent-induced disproportionation; thus the overall process remains a one-electron reaction rather than an overall two-electron oxidative addition process, even under long time-scale, bulk electrolysis conditions. Chemical oxidation of [cat](4)[Pt(2)(mu-pop)(4)] with [NO][BF(4)] or AgBF(4) gives mainly a dark, insoluble, ill-defined solid that appears to contain Pt(III) according to X-ray photoelectron spectroscopy (XPS). In the case of [NO][BF(4)], a second reaction product, an orange solid, has been identified as a nitrosyl complex, [cat](3)[Pt(2)(mu-pop)(4)(NO)]. The X-ray structure of the PPN(+) salt shows the anion to consist of the usual lantern-shaped Pt(2)(mu-pop)(4) framework with an unusually large Pt-Pt separation [2.8375(6) A]; one of the platinum atoms carries a bent nitrosyl group [r(N-O) = 1.111(15) A; angle(Pt-N-O) = 118.1(12) degrees] occupying an axial position. The nitrosyl group migrates rapidly on the (31)P NMR time-scale between the metal atoms at room temperature but the motion is slow enough at 183 K that the expected two pairs of inequivalent phosphorus nuclei can be observed. The X-ray photoelectron (XP) spectrum of the nitrosyl-containing anion confirms the presence of two inequivalent platinum atoms whose 4f(7/2) binding energies are in the ranges expected for Pt(II) and Pt(III); an alternative interpretation is that the second platinum atom has a formal oxidation number of +4 and that its binding energy is modified by the strongly sigma-donating NO(-) ligand. Reduction of [Pt(2)(mu-pop)(4)X(2)](4-) (X = Cl, Br, I) in dichloromethane corresponds to a chemically reversible, electrochemically irreversible two-electron process involving loss of halide and formation of [Pt(2)(mu-pop)(4)](4-), as is the case in more strongly coordinating solvents. PMID:19226168

  5. History of the paired lunar meteorites MAC88104 and MAC88105 derived from noble gas isotopes, radionuclides, and some chemical abundances

    SciTech Connect

    Eugster, O.; Burger, M.; Kraehenbuehl, U.; Michel, T. ); Beer, J. ); Finkel, R.C. ); Hofmann, H.J.; Synal, H.A.; Woelfli, W. )

    1991-11-01

    Noble gas isotopes, radionuclides, and chemical abundances were studied in the lunar meteorites MAC88104 and MAC88105 collected in the MacAlpine Hills area of Antarctica. The concentrations of the noble gas isotopes and the radionuclide activities in the two meteorites are essentially identical, proving that the two meteorites are paired. From {sup 40}K-{sup 40}Ar dating the authors obtain a gas retention age of 3,550 {plus minus} 400 Ma, typical for lunar surface material. Probably before breccia compaction the MAC88104/5 material resided for 630 {plus minus} 200 Ma at an average shielding depth of 85 g/cm{sup 2}, that is, about 50 cm below the lunar surface in the lunar regolith, as judged from the concentration of cosmic-ray produced Kr and Xe isotopes. Although this duration of lunar regolith residence is relatively long, MAC88104/5 represent immature regolith material: the concentration of solar wind implanted noble gases are two orders of magnitude lower than those in mature lunar soil. The {sup 40}Ar/{sup 36}Ar ratio of the trapped component is 5.7 {plus minus} 1.0, indicating an intermediate antiquity of the material; the authors estimate that the solar wind and lunar atmospheric particles were implanted about 2,000 Ma ago. The radionuclide activities allow a determination of the exposure history of the MAC88104/5 material. The duration of the Moon-Earth transfer was {much lt} 0.24 Ma. The exposure histories of the lunar meteorites discussed in this work indicate that at least two impact events are required for their ejection from the Moon. The authors first noble gas results for lunar meteorite Yamato-793274 show that it represents mature lunar regolith material with relatively high concentrations of solar wind implanted noble gas and a duration of several hundred million years of exposure to cosmic rays.

  6. Systemic Approaches Identify a Garlic-Derived Chemical, Z-ajoene, as a Glioblastoma Multiforme Cancer Stem Cell-Specific Targeting Agent

    PubMed Central

    Jung, Yuchae; Park, Heejoo; Zhao, Hui-Yuan; Jeon, Raok; Ryu, Jae-Ha; Kim, Woo-Young

    2014-01-01

    Glioblastoma multiforme (GBM) is one of the most common brain malignancies and has a very poor prognosis. Recent evidence suggests that the presence of cancer stem cells (CSC) in GBM and the rare CSC subpopulation that is resistant to chemotherapy may be responsible for the treatment failure and unfavorable prognosis of GBM. A garlic-derived compound, Z-ajoene, has shown a range of biological activities, including anti-proliferative effects on several cancers. Here, we demonstrated for the first time that Z-ajoene specifically inhibits the growth of the GBM CSC population. CSC sphere-forming inhibition was achieved at a concentration that did not exhibit a cytotoxic effect in regular cell culture conditions. The specificity of this inhibitory effect on the CSC population was confirmed by detecting CSC cell surface marker CD133 expression and biochemical marker ALDH activity. In addition, stem cell-related mRNA profiling and real-time PCR revealed the differential expression of CSC-specific genes, including Notch, Wnt, and Hedgehog, upon treatment with Z-ajoene. A proteomic approach, i.e., reverse-phase protein array (RPPA) and Western blot analysis, showed decreased SMAD4, p-AKT, 14.3.3 and FOXO3A expression. The protein interaction map (http://string-db.org/) of the identified molecules suggested that the AKT, ERK/p38 and TGFβ signaling pathways are key mediators of Z–ajoene’s action, which affects the transcriptional network that includes FOXO3A. These biological and bioinformatic analyses collectively demonstrate that Z-ajoene is a potential candidate for the treatment of GBM by specifically targeting GBM CSCs. We also show how this systemic approach strengthens the identification of new therapeutic agents that target CSCs. PMID:25078449

  7. Systemic approaches identify a garlic-derived chemical, Z-ajoene, as a glioblastoma multiforme cancer stem cell-specific targeting agent.

    PubMed

    Jung, Yuchae; Park, Heejoo; Zhao, Hui-Yuan; Jeon, Raok; Ryu, Jae-Ha; Kim, Woo-Young

    2014-07-01

    Glioblastoma multiforme (GBM) is one of the most common brain malignancies and has a very poor prognosis. Recent evidence suggests that the presence of cancer stem cells (CSC) in GBM and the rare CSC subpopulation that is resistant to chemotherapy may be responsible for the treatment failure and unfavorable prognosis of GBM. A garlic-derived compound, Z-ajoene, has shown a range of biological activities, including anti-proliferative effects on several cancers. Here, we demonstrated for the first time that Z-ajoene specifically inhibits the growth of the GBM CSC population. CSC sphere-forming inhibition was achieved at a concentration that did not exhibit a cytotoxic effect in regular cell culture conditions. The specificity of this inhibitory effect on the CSC population was confirmed by detecting CSC cell surface marker CD133 expression and biochemical marker ALDH activity. In addition, stem cell-related mRNA profiling and real-time PCR revealed the differential expression of CSC-specific genes, including Notch, Wnt, and Hedgehog, upon treatment with Z-ajoene. A proteomic approach, i.e., reverse-phase protein array (RPPA) and Western blot analysis, showed decreased SMAD4, p-AKT, 14.3.3 and FOXO3A expression. The protein interaction map (http://string-db.org/) of the identified molecules suggested that the AKT, ERK/p38 and TGFβ signaling pathways are key mediators of Z-ajoene's action, which affects the transcriptional network that includes FOXO3A. These biological and bioinformatic analyses collectively demonstrate that Z-ajoene is a potential candidate for the treatment of GBM by specifically targeting GBM CSCs. We also show how this systemic approach strengthens the identification of new therapeutic agents that target CSCs. PMID:25078449

  8. Chemical modification of ascorbic acid and evaluation of its lipophilic derivatives as inhibitors of secretory phospholipase A(2) with anti-inflammatory activity.

    PubMed

    Mohamed, Riyaz; Dharmappa, K K; Tarannum, Shaista; Jameel, N M; Kannum, S A; Ashrafulla, H S; Rai, Lokanath; Souza, Cletus Jmd'; Shekhar, M A; Vishwanath, Bannikuppe S

    2010-12-01

    The halo 6-fatty acid esters of L-ascorbic acid 3a, 3b and 6-fatty acid esters of L-ascorbic acid 5a-g were achieved from L-ascorbic acid 1. Compounds 3a, 3b and 5a-g were evaluated for anti-oxidant, anti-lipid peroxidation, and secretory phospholipase A(2) (sPLA(2)) inhibition in vitro, and sPLA(2) induced mouse paw edema. All the derivatives retained their anti-oxidant property compared to ascorbic acid at 6 × 10(-4)M and are good inhibitors of lipid peroxidation at 1 mg ml(-1) as evaluated by 2, 2-Diphenyl-1-picrylhydrazyl radical and thio-barbituric acid methods, respectively. Compounds 5e and 5f significantly inhibited purified group I sPLA(2) from Naja naja and group II sPLA(2) from Vipera russelli, human synovial fluid and human pleural fluid with IC(50) value ranging from 64 ± 1.95 to 82 ± 1.3 and 48 ± 2.27 to 61 ± 2.23 μM, respectively. The compounds 5e and 5f also showed varying degree of potency in neutralizing indirect hemolytic activity of sPLA(2) at 50 μM concentration, and sPLA(2) induced mouse paw edema at the dose 3 mg/kg. Further docking studies also confirmed that compounds 5e and 5f have maximum interaction with increasing negative energy value. Single molecule possessing both anti-oxidant and anti-inflammatory activities is of great therapeutic significance in inflammatory disorders. PMID:20730622

  9. Evaluating Whole Chemical Mixtures and Sufficient Similarity

    EPA Science Inventory

    This powerpoint presentation supports apresentation describing dose-response assessment for complex chemical mixtures including deriving reference doses for mixtures evaluating sufficient similarity among chemical mixtures.

  10. Quantitative NMR-derived interproton distances combined with quantum mechanical calculations of 13C chemical shifts in the stereochemical determination of conicasterol F, a nuclear receptor ligand from Theonella swinhoei.

    PubMed

    Chini, Maria Giovanna; Jones, Catharine R; Zampella, Angela; D'Auria, Maria Valeria; Renga, Barbara; Fiorucci, Stefano; Butts, Craig P; Bifulco, Giuseppe

    2012-02-01

    Here we report the first application of combined accurate ROE-distance analysis with DFT calculations of NMR chemical shifts to achieve the relative configuration assignment of a marine natural product, conicasterol F, a new polyhydroxylated steroid isolated from the marine sponge Theonella swinhoei. We demonstrate the substantial advantages of this combined approach as a tool for structural studies of natural products, providing a powerful alternative to, or information to underpin, total synthesis when more classical NMR data analysis fails to provide unequivocal results. In this paper, we also describe the isolation and structure elucidation of conicasterol F and its 24-ethyl derivative, theonellasterol I, and their pharmacological evaluation as human nuclear receptor modulators. PMID:22201476

  11. Optimization of water treatment methods for the purification of peat extraction derived runoff: Evaluation of chemical treatment response to variations in incoming water quality using a 2k factorial test design

    NASA Astrophysics Data System (ADS)

    Heiderscheidt, Elisangela; Ronkanen, Anna-Kaisa; Klöve, Björn

    2013-04-01

    The sustainable use of peatland areas requires measures to minimize and when possible eradicate the identified environmental impacts. The drainage of peatlands and other peat extraction, agriculture and forestry activities are known to increase the leaching of pollutant substances resulting in the eutrophication and siltation of receiving water bodies, causing water quality deterioration. Due to the geochemistry characteristics of peat soils the quality of peatland derived runoff water is known to oscillate with location and also with variations in runoff and peak discharge occurrences. Affordable, simple and reliable purification methods that can purify waters rich in particulates, nutrients and dissolved organic carbon while capable of coping with incoming water quality variations are therefore required. Chemical treatment is considered one of the best available technologies for the purification of peat extraction runoff water in Finland; however, until recently little research had been applied on the development of this treatment method for the purification of non-point source pollution. Chemical purification, using metal salts as coagulant agents, is currently applied in several treatment facilities in Finnish peat extraction sites. Nevertheless, variations in runoff water quality and the lack of development of field process parameters has led to the application of high chemical dosages, significant and undesirable fluctuations in purification efficiency and high metal concentration in the discharging waters. This work aims to develop and optimize the chemical purification method by using high level scientific methods to evaluate the response of the purification process to variations in water quality which are typical of peatland derived runoff. The evaluation of how the purification process responds to these variations is a critical step which will enable the development of preventive measures and optimization of relevant process parameters and thus reduce the environmental impacts related to this treatment method. The influence of variations in water quality parameters was accessed using a 2k factorial test design and a well-known chemical purification pilot test procedure (jar test). The k factors or parameters evaluated were: organic matter as chemical oxygen demand (COD 20mg/l and 80mg/l), suspended solids (SS 10mg/l and 60 mg/l), applied coagulant dosage (ferric sulphate 35mg/l and 100mg/l) as well as pH (4.5 and 7.0). Water samples were collected from different peat extraction sites and suitable samples were manipulated using techniques such as centrifugation, dilution and acid or base addition to produce samples with the combinations of high and low concentrations presented. The complete statistical analysis of obtained results will include evaluation of variability using the univariate repeated measures ANOVA as well as the multivariate repeated measures ANOVA methods. Preliminary results of the univariate analyses shows that the interaction between the concentration of a particular substance (COD, SS and pH) and the dosage applied impose significant higher influence on the overall purification efficiency than the substance concentration and applied dosage as individual factors.

  12. 40 CFR 721.1820 - Bisphenol derivative.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Bisphenol derivative. 721.1820 Section... Substances § 721.1820 Bisphenol derivative. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as bisphenol derivative (PMN No. P-92-509)...

  13. 40 CFR 721.1820 - Bisphenol derivative.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Bisphenol derivative. 721.1820 Section... Substances § 721.1820 Bisphenol derivative. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as bisphenol derivative (PMN No. P-92-509)...

  14. 40 CFR 721.1820 - Bisphenol derivative.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Bisphenol derivative. 721.1820 Section... Substances § 721.1820 Bisphenol derivative. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as bisphenol derivative (PMN No. P-92-509)...

  15. 40 CFR 721.1820 - Bisphenol derivative.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Bisphenol derivative. 721.1820 Section... Substances § 721.1820 Bisphenol derivative. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as bisphenol derivative (PMN No. P-92-509)...

  16. 40 CFR 721.1820 - Bisphenol derivative.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Bisphenol derivative. 721.1820 Section... Substances § 721.1820 Bisphenol derivative. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as bisphenol derivative (PMN No. P-92-509)...

  17. 40 CFR 721.9658 - Thiadiazole derivative.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Thiadiazole derivative. 721.9658... Substances § 721.9658 Thiadiazole derivative. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as a thiadiazole derivative (PMN P-94-1631) is subject...

  18. 40 CFR 721.5913 - Phenothiazine derivative.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Phenothiazine derivative. 721.5913... Substances § 721.5913 Phenothiazine derivative. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as a phenothiazine derivative (PMN P-96-813)...

  19. 40 CFR 721.5913 - Phenothiazine derivative.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Phenothiazine derivative. 721.5913... Substances § 721.5913 Phenothiazine derivative. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as a phenothiazine derivative (PMN P-96-813)...

  20. 40 CFR 721.5913 - Phenothiazine derivative.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Phenothiazine derivative. 721.5913... Substances § 721.5913 Phenothiazine derivative. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as a phenothiazine derivative (PMN P-96-813)...

  1. 40 CFR 721.5913 - Phenothiazine derivative.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Phenothiazine derivative. 721.5913... Substances § 721.5913 Phenothiazine derivative. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as a phenothiazine derivative (PMN P-96-813)...

  2. 40 CFR 721.5913 - Phenothiazine derivative.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Phenothiazine derivative. 721.5913... Substances § 721.5913 Phenothiazine derivative. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as a phenothiazine derivative (PMN P-96-813)...

  3. Oxygenated Derivatives of Hydrocarbons

    Technology Transfer Automated Retrieval System (TEKTRAN)

    For the book entitled “Insect Hydrocarbons: Biology, Biochemistry and Chemical Ecology”, this chapter presents a comprehensive review of the occurrence, structure and function of oxygenated derivatives of hydrocarbons. The book chapter focuses on the occurrence, structural identification and functi...

  4. Biotechnology and derived products

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Microorganisms able to infect and kill insect pests, metabolites from plants and microorganisms, and transgenic crops are biotechnologically derived products that are being promoted for use to control insect pests in lieu of chemical insecticides. Products based on these technologies effectively co...

  5. Radical-assisted chemical doping for chemically derived graphene

    PubMed Central

    2013-01-01

    Carrier doping of graphene is one of the most challenging issues that needs to be solved to enable its use in various applications. We developed a carrier doping method using radical-assisted conjugated organic molecules in the liquid phase and demonstrated all-wet fabrication process of doped graphene films without any vacuum process. Charge transfer interaction between graphene and dopant molecules was directly investigated by spectroscopic studies. The resistivity of the doped graphene films was drastically decreased by two orders of magnitude. The resistivity was improved by not only carrier doping but the improvement in adhesion of doped graphene flakes. First-principles calculation supported the model of our doping mechanism. PMID:24355062

  6. Inquiry of the electron density transfers in chemical reactions: a complete reaction path for the denitrogenation process of 2,3-diazabicyclo[2.2.1]hept-2-ene derivatives.

    PubMed

    Safont, Vicent S; González-Navarrete, Patricio; Oliva, Mónica; Andrés, Juan

    2015-12-28

    A detailed study on all stages associated with the reaction mechanisms for the denitrogenation of 2,3-diazabicyclo[2.2.1]hept-2-ene derivatives (DBX, with X substituents at the methano-bridge carbon atom, X = H and OH) is presented. In particular, we have characterized the processes leading to cycloalkene derivatives through migration-type mechanisms as well as the processes leading to cyclopentil-1,3-diradical species along concerted or stepwise pathways. The reaction mechanisms have been further analysed within the bonding evolution theory framework at B3LYP and M05-2X/6-311+G(2d,p) levels of theory. Analysis of the results allows us to obtain the intimate electronic mechanism for the studied processes, providing a new topological picture of processes underlying the correlation between the experimental measurements obtained by few-optical-cycle visible pulse radiation and the quantum topological analysis of the electron localization function (ELF) in terms of breaking/forming processes along this chemical rearrangement. The evolution of the population of the disynaptic basin V(N1,N2) can be related to the experimental observation associated with the N=N stretching mode evolution, relative to the N2 release, along the reaction process. This result allows us to determine why the N2 release is easier for the DBH case via a concerted mechanism compared to the stepwise mechanism found in the DBOH system. This holds the key to unprecedented insight into the mapping of the electrons making/breaking the bonds while the bonds change. PMID:26584857

  7. Chemical and biological characterisation of sapinopyridione, a phytotoxic 3,3,6-trisubstituted-2,4-pyridione produced by Sphaeropsis sapinea, a toxigenic pathogen of native and exotic conifers, and its derivatives.

    PubMed

    Evidente, Antonio; Fiore, Michele; Bruno, Giovanni; Sparapano, Lorenzo; Motta, Andrea

    2006-05-01

    A phytotoxic trisubstituted 2,4-pyridione, named sapinopyridione, was isolated from the culture filtrates of Sphaeropsis sapinea, a fungal pathogen of conifers occurring world-wide. Three strains were isolated from two cypress species. Strain D-55 isolated from Cupressus sempervirens resulted high producer of sapinopyridione (12.3 mg l(-1)), whereas strain D-54 isolated from the same cypress species was low producer (1.1 mg l(-1)); strain D-50 isolated from C. macrocarpa was intermediate producer (5.4 mg l(-1)). Sapinopyridione was characterised by spectroscopic and chemical methods, as the 6-methyl-2-(2-methyl-1-oxobutyl)-1-oxa-5-azaspiro[2.5]oct-6-ene-4,8-dione. The structure was supported by the preparation of three key derivatives, whose phytotoxic and antimycotic activities were also tested on host plants and on three Seiridium species, virulent fungal agents of cypress canker disease. Some structure-activity relationships were identified for both phytoxicity and antifungal activities. These activities appear related to the presence of both pyridione and oxiran rings. Also the carbonyl group of the side chain seems to play a role into impart activity. PMID:16712886

  8. [Azoles. 18. Sulfonylindazole derivatives].

    PubMed

    Dudzińska-Usarewicz, J; Wrzeciono, U; Frankiewicz, A; Linkowska, E; Köhler, T; Nuhn, P

    1988-09-01

    The nucleophilic substitution of hydrogen to synthesize the sulphonyl indazole derivatives 9-16 is described. The structures of the substitution products are discussed using H-NMR spectra. Chemical structural proof was given by steric hindrance observed in the process of chorination of 9-16. The compounds 3, 4, 7, 8, 14, and 16 are studied to find an inhibition on phospholipase-A2 and lipoxygenase-I. PMID:3149748

  9. Chemical Emergencies

    MedlinePlus

    Chemical Emergencies Under certain conditions, chemicals which are normally safe can be poisonous or harmful to your health. A major chemical emergency is an accident that releases a hazardous amount ...

  10. Derivative chameleons

    SciTech Connect

    Noller, Johannes

    2012-07-01

    We consider generalized chameleon models where the conformal coupling between matter and gravitational geometries is not only a function of the chameleon field φ, but also of its derivatives via higher order co-ordinate invariants (such as ∂{sub μ}φ∂{sup μ}φ,□φ,...). Specifically we consider the first such non-trivial conformal factor A(φ,∂{sub μ}φ∂{sup μ}φ). The associated phenomenology is investigated and we show that such theories have a new generic mass-altering mechanism, potentially assisting the generation of a sufficiently large chameleon mass in dense environments. The most general effective potential is derived for such derivative chameleon setups and explicit examples are given. Interestingly this points us to the existence of a purely derivative chameleon protected by a shift symmetry for φ → φ+c. We also discuss potential ghost-like instabilities associated with mass-lifting mechanisms and find another, mass-lowering and instability-free, branch of solutions. This suggests that, barring fine-tuning, stable derivative models are in fact typically anti-chameleons that suppress the field's mass in dense environments. Furthermore we investigate modifications to the thin-shell regime and prove a no-go theorem for chameleon effects in non-conformal geometries of the disformal type.

  11. LLNL Chemical Kinetics Modeling Group

    SciTech Connect

    Pitz, W J; Westbrook, C K; Mehl, M; Herbinet, O; Curran, H J; Silke, E J

    2008-09-24

    The LLNL chemical kinetics modeling group has been responsible for much progress in the development of chemical kinetic models for practical fuels. The group began its work in the early 1970s, developing chemical kinetic models for methane, ethane, ethanol and halogenated inhibitors. Most recently, it has been developing chemical kinetic models for large n-alkanes, cycloalkanes, hexenes, and large methyl esters. These component models are needed to represent gasoline, diesel, jet, and oil-sand-derived fuels.

  12. The chemical juggernaut.

    PubMed

    Cadbury, D

    1997-01-01

    Man-made chemicals pervade and support every aspect of modern living. The chemical industry has become such a powerful force in the global economy, sales of synthetic chemicals and products derived from them constitute well in excess of a third of the world's gross national product. But, these man-made chemicals are also 'elixirs of death,' the symbol of human destruction. Laboratory tests have shown that a number of chemicals in common use possess a remarkable property: they can weakly mimic or modify the action of human hormones. It has been proven that some chemicals found in plastics, pesticides, and industrial products are weakly estrogenic, modifying the action of the female hormone. In addition, other chemicals affect the male hormones, androgens, or anti-androgens; others are thought to target different hormone systems, such as thyroid and adrenal glands. Many research studies are being conducted to establish the impact of chemicals on human health. Of special concern are the rising incidence of testicular cancer, decline in human sperm counts, and the sharp rise of breast cancer. In conclusion, although there is a worldwide debate on the effects of chemical exposure on humans, the significance of findings for human health, concerning testicular and breast cancer, are still unknown. An international treaty is called for to control the use of the persistent hormonally active chemicals. PMID:12321044

  13. Biomass, Chemicals from

    SciTech Connect

    Elliott, Douglas C.

    2004-03-15

    This chapter describes the use and potential use of biomass resources for chemical production as a means to displace petroleum use. Therefore, the scope of the discussion is limited to large scale, commodity chemical products that can have an impact on the energy market by displacing petroleum conversion to chemical products. This article does not address in detail specialty chemical products whose limited market would have minimal impact on energy markets; nor does it describe in detail the use of biomass for material products such as cellulosic fiber for paper or lignocellulosic material for construction materials. The use of biomass for production of a vast array of specialty chemicals based on unique biochemical structures is another part of the overall concept of a sustainable economy, but is outside the scope of this article. Chemical production from biomass is an energy issue in that biomass-derived chemicals can result in a significant impact on the petroleum requirement for petrochemicals used in modern society. Petroleum thus displaced is available for use in the energy market. Petroleum utilization for chemicals production is reported at 14% of the petroleum market in the United States. Displacement of a significant fraction of this chemical synthesis from petroleum can provide an important impact on the overall market. In 1998 the U.S. Department of Energy stated as its goal the production of at least 10% of the basic chemical building blocks from plant-derived renewables by the year 2020 (a five-fold increase) and 50% by 2050 (another five-fold increase). In the long run, utilization of renewable carbon sources for the chemical requirements of society is the only option as fossil sources become more scarce.

  14. Complex derivatives

    NASA Astrophysics Data System (ADS)

    Battiston, Stefano; Caldarelli, Guido; Georg, Co-Pierre; May, Robert; Stiglitz, Joseph

    2013-03-01

    The intrinsic complexity of the financial derivatives market has emerged as both an incentive to engage in it, and a key source of its inherent instability. Regulators now faced with the challenge of taming this beast may find inspiration in the budding science of complex systems.

  15. Semisynthetic Derivatives of Epothilones

    NASA Astrophysics Data System (ADS)

    Altmann, Karl-Heinz

    Semisynthetic derivatives of natural products traditionally occupy a prominent space in natural-product-based drug discovery (1, 2). As many biologically active natural products exhibit a high degree of structural complexity (3), the chemical derivatization of material isolated from natural sources often represents the only feasible means (or at least the only economically viable approach) to explore structure-activity-relationships (SAR) and to produce analogs with more favorable pharmacokinetic and pharmacological properties than the natural product lead. Examples of clinically important drugs that are semisynthetic derivatives of natural products exist in virtually all disease areas (1, 2); in the treatment of cancer this includes compounds such as etoposide or teniposide (derived from podophyllotoxin) (4-6), irinotecan and topotecan (derived from camptothecin) (7-9), or docetaxel (derived from 10-deacetylbaccatin III) (10, 11). Even for taxol (11), which is a natural product (12), the sustained supply of sufficient quantities of material for widespread clinical use could only be secured through the development of a semisynthetic production process from another natural product, namely, 10-deacetylbaccatin III (13). In light of these facts, it is not surprising that semisynthesis approaches have also featured prominently in the elucidation of the SAR for epothilones and in the discovery of a number of clinical development candidates.

  16. Chemical Microsensors For Detection Of Explosives And Chemical Warfare Agents

    SciTech Connect

    Yang, Xiaoguang; Swanson, Basil I.

    2001-11-13

    An article of manufacture is provided including a substrate having an oxide surface layer and a layer of a cyclodextrin derivative chemically bonded to said substrate, said layer of a cyclodextrin derivative adapted for the inclusion of selected compounds, e.g., nitro-containing organic compounds, therewith. Such an article can be a chemical microsensor capable of detecting a resultant mass change from inclusion of the nitro-containing organic compound.

  17. Chemical Specific Adjustment factors Workshop

    EPA Science Inventory

    The World Health Organization, through the International Programme on Chemical Safety (IPCS), has established guidance on the use of mechanistic data to replace default uncertainty factors for interspecies extrapolation and intraspecies variability in deriving risk values such as...

  18. Chemical Specific Adjustment Factors Workshop

    EPA Science Inventory

    The World Health Organization, through the International Programme on Chemical Safety (IPCS), has established guidance on the use of mechanistic data to replace default uncertainty factors for interspecies extrapolation and intraspecies variability in deriving risk values such as...

  19. An Elementary Discussion of Chemical Equilibrium.

    ERIC Educational Resources Information Center

    David, Carl W.

    1988-01-01

    This discussion uses a more difficult reaction as the prototype to derive the standard equation for chemical equilibrium. It can be used by students who can understand and use partial derivatives. (CW)

  20. Chemical sensor

    NASA Technical Reports Server (NTRS)

    Rauh, R. David (Inventor)

    1990-01-01

    A sensor for detecting a chemical substance includes an insertion element having a structure which enables insertion of the chemical substance with a resulting change in the bulk electrical characteristics of the insertion element under conditions sufficient to permit effective insertion; the change in the bulk electrical characteristics of the insertion element is detected as an indication of the presence of the chemical substance.

  1. 40 CFR 721.10317 - Alkyl phosphate derivative (generic).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Alkyl phosphate derivative (generic... Specific Chemical Substances § 721.10317 Alkyl phosphate derivative (generic). (a) Chemical substance and... phosphate derivative (PMN P-02-1040) is subject to reporting under this section for the significant new...

  2. 40 CFR 721.10317 - Alkyl phosphate derivative (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Alkyl phosphate derivative (generic... Specific Chemical Substances § 721.10317 Alkyl phosphate derivative (generic). (a) Chemical substance and... phosphate derivative (PMN P-02-1040) is subject to reporting under this section for the significant new...

  3. 40 CFR 721.10317 - Alkyl phosphate derivative (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Alkyl phosphate derivative (generic... Specific Chemical Substances § 721.10317 Alkyl phosphate derivative (generic). (a) Chemical substance and... phosphate derivative (PMN P-02-1040) is subject to reporting under this section for the significant new...

  4. 40 CFR 721.5925 - Bis heterocyclic phenylene derivative (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Bis heterocyclic phenylene derivative... Specific Chemical Substances § 721.5925 Bis heterocyclic phenylene derivative (generic). (a) Chemical... as bis heterocyclic phenylene derivative (PMN P-01-0432) is subject to reporting under this...

  5. 40 CFR 721.5925 - Bis heterocyclic phenylene derivative (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Bis heterocyclic phenylene derivative... Specific Chemical Substances § 721.5925 Bis heterocyclic phenylene derivative (generic). (a) Chemical... as bis heterocyclic phenylene derivative (PMN P-01-0432) is subject to reporting under this...

  6. 40 CFR 721.5925 - Bis heterocyclic phenylene derivative (generic).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Bis heterocyclic phenylene derivative... Specific Chemical Substances § 721.5925 Bis heterocyclic phenylene derivative (generic). (a) Chemical... as bis heterocyclic phenylene derivative (PMN P-01-0432) is subject to reporting under this...

  7. 40 CFR 721.5925 - Bis heterocyclic phenylene derivative (generic).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Bis heterocyclic phenylene derivative... Specific Chemical Substances § 721.5925 Bis heterocyclic phenylene derivative (generic). (a) Chemical... as bis heterocyclic phenylene derivative (PMN P-01-0432) is subject to reporting under this...

  8. 40 CFR 721.9079 - Dihydro quinacridone derivative (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Dihydro quinacridone derivative... Specific Chemical Substances § 721.9079 Dihydro quinacridone derivative (generic). (a) Chemical substance... dihydro quinacridone derivative (PMN P-01-397) is subject to reporting under this section for...

  9. 40 CFR 721.646 - Aminofluoran derivative (generic name).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Aminofluoran derivative (generic name... Substances § 721.646 Aminofluoran derivative (generic name). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as aminofluoran derivative (PMN...

  10. 40 CFR 721.2025 - Substituted phenylimino carbamate derivative.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... derivative. 721.2025 Section 721.2025 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED... Specific Chemical Substances § 721.2025 Substituted phenylimino carbamate derivative. (a) Chemical... as a substituted phenylimino carbamate derivative (PMN P-91-487) is subject to reporting under...

  11. 40 CFR 721.10172 - Alkylamide derivative (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Alkylamide derivative (generic). 721... Substances § 721.10172 Alkylamide derivative (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as alkylamide derivative (PMN...

  12. 40 CFR 721.5925 - Bis heterocyclic phenylene derivative (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Bis heterocyclic phenylene derivative... Specific Chemical Substances § 721.5925 Bis heterocyclic phenylene derivative (generic). (a) Chemical... as bis heterocyclic phenylene derivative (PMN P-01-0432) is subject to reporting under this...

  13. 40 CFR 721.6097 - Phosphoric acid derivative (generic name).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Phosphoric acid derivative (generic... Specific Chemical Substances § 721.6097 Phosphoric acid derivative (generic name). (a) Chemical substance... phosphoric acid derivative (PMN P-95-284) is subject to reporting under this section for the significant...

  14. [Chemical weapons and chemical terrorism].

    PubMed

    Nakamura, Katsumi

    2005-10-01

    Chemical Weapons are kind of Weapons of Mass Destruction (WMD). They were used large quantities in WWI. Historically, large quantities usage like WWI was not recorded, but small usage has appeared now and then. Chemical weapons are so called "Nuclear weapon for poor countrys" because it's very easy to produce/possession being possible. They are categorized (1) Nerve Agents, (2) Blister Agents, (3) Cyanide (blood) Agents, (4) Pulmonary Agents, (5) Incapacitating Agents (6) Tear Agents from the viewpoint of human body interaction. In 1997 the Chemical Weapons Convention has taken effect. It prohibits chemical weapons development/production, and Organization for the Prohibition of Chemical Weapons (OPCW) verification regime contributes to the chemical weapons disposal. But possibility of possession/use of weapons of mass destruction by terrorist group represented in one by Matsumoto and Tokyo Subway Sarin Attack, So new chemical terrorism countermeasures are necessary. PMID:16296384

  15. Chemical Composition

    NASA Astrophysics Data System (ADS)

    May, Willie; Cavanagh, Richard; Turk, Gregory; Winchester, Michael; Travis, John; Smith, Melody; Derose, Paul; Choquette, Steven; Kramer, Gary; Sieber, John; Greenberg, Robert; Lindstrom, Richard; Lamaze, George; Zeisler, Rolf; Schantz, Michele; Sander, Lane; Phinney, Karen; Welch, Michael; Vetter, Thomas; Pratt, Kenneth; Scott, John; Small, John; Wight, Scott; Stranick, Stephan

    Measurements of the chemical compositions of materials and the levels of certain substances in them are vital when assessing and improving public health, safety and the environment, are necessary to ensure trade equity, and are required when monitoring and improving industrial products and services. Chemical measurements play a crucial role in most areas of the economy, including healthcare, food and nutrition, agriculture, environmental technologies, chemicals and materials, instrumentation, electronics, forensics, energy, and transportation.

  16. Chemical sensors

    DOEpatents

    Lowell, Jr., James R.; Edlund, David J.; Friesen, Dwayne T.; Rayfield, George W.

    1991-01-01

    Sensors responsive to small changes in the concentration of chemical species are disclosed, comprising (a) a mechanochemically responsive polymeric film capable of expansion or contraction in response to a change in its chemical environment, operatively coupled to (b) a transducer capable of directly converting said expansion or contraction to a measurable electrical response.

  17. Chemical preconcentrator

    DOEpatents

    Manginell, Ronald P.; Frye-Mason, Gregory C.

    2001-01-01

    A chemical preconcentrator is disclosed with applications to chemical sensing and analysis. The preconcentrator can be formed by depositing a resistive heating element (e.g. platinum) over a membrane (e.g. silicon nitride) suspended above a substrate. A coating of a sorptive material (e.g. a microporous hydrophobic sol-gel coating or a polymer coating) is formed on the suspended membrane proximate to the heating element to selective sorb one or more chemical species of interest over a time period, thereby concentrating the chemical species in the sorptive material. Upon heating the sorptive material with the resistive heating element, the sorbed chemical species are released for detection and analysis in a relatively high concentration and over a relatively short time period. The sorptive material can be made to selectively sorb particular chemical species of interest while not substantially sorbing other chemical species not of interest. The present invention has applications for use in forming high-sensitivity, rapid-response miniaturized chemical analysis systems (e.g. a "chem lab on a chip").

  18. Chemical sensors

    DOEpatents

    Lowell, J.R. Jr.; Edlund, D.J.; Friesen, D.T.; Rayfield, G.W.

    1991-07-02

    Sensors responsive to small changes in the concentration of chemical species are disclosed. The sensors comprise a mechanochemically responsive polymeric film capable of expansion or contraction in response to a change in its chemical environment. They are operatively coupled to a transducer capable of directly converting the expansion or contraction to a measurable electrical response. 9 figures.

  19. Chemical plume source localization.

    PubMed

    Pang, Shuo; Farrell, Jay A

    2006-10-01

    This paper addresses the problem of estimating a likelihood map for the location of the source of a chemical plume using an autonomous vehicle as a sensor probe in a fluid flow. The fluid flow is assumed to have a high Reynolds number. Therefore, the dispersion of the chemical is dominated by turbulence, resulting in an intermittent chemical signal. The vehicle is capable of detecting above-threshold chemical concentration and sensing the fluid flow velocity at the vehicle location. This paper reviews instances of biological plume tracing and reviews previous strategies for a vehicle-based plume tracing. The main contribution is a new source-likelihood mapping approach based on Bayesian inference methods. Using this Bayesian methodology, the source-likelihood map is propagated through time and updated in response to both detection and nondetection events. Examples are included that use data from in-water testing to compare the mapping approach derived herein with the map derived using a previously existing technique. PMID:17036813

  20. Radioiodinated estrogen derivatives

    SciTech Connect

    Mazaitis, J.K.; Gibson, R.E.; Komai, T.; Eckelman, W.C.; Francis, B.; Reba, R.C.

    1980-02-01

    Monoiodohexestrol exhibits 10 to 15% specific binding to the 8S estrogen receptor while the remainder binds to nonreceptor 4S proteins. Reduction of nonreceptor binding with either thyroxine or 8-anilino-1-naphthalene sulfonic acid was not quantitative. Thus no accurate determination of the concentration of receptor sites in the radioreceptor assay was possible by graphical analysis. Two additional estrogens-17..cap alpha..-(/sup 125/I)iodoethynylestradiol and 17..cap alpha..-(/sup 125/I)iodoethynyl-11..beta..-methoxy estradiol - were synthesized at high specific activity. Although the iodoethynyl derivatives were stable under synthetic conditions, deiodination in the presence of proteins is too fast to allow either in vivo or in vitro use. To make these compounds clinically useful, therefore, chemical modification to reduce nonreceptor binding and the rate of dehalogenation must be undertaken.

  1. Comprehensive report on nuclear medicine, March 1, 1980-February 28, 1983. [Radioiodination of. omega. -iodo-fatty acids and estradiol derivatives; chemical preparation of /sup 13/N-amines

    SciTech Connect

    Kabalka, G.W.

    1983-01-01

    The long-range objective is to develop new rapid methods for the introduction of short-lived radionuclides into agents for use in diagnostic nuclear medicine. During the initial three-year period, syntheses of radioiodine-labeled ..omega..-iodo-fatty acids and radioiodine-labeled estradiol derivatives were accomplished. Furthermore, synthetic routes to nitrogen-13-labeled amines were investigated. The synthetic routes involved organoborane intermediates which produce good yields of high-specific-activity radiolabeled products in reasonable reaction times. In addition, the incorporation of other nuclides (Cl, F, Br, O, and C) which have medically important isotopes was investigated. Results of the 3-year study are summarized.

  2. Unnecessary Chemicals

    ERIC Educational Resources Information Center

    Johnson, Anita

    1978-01-01

    Discusses the health hazards resulting from chemical additions of many common products such as cough syrups, food dyes, and cosmetics. Steps being taken to protect consumers from these health hazards are included. (MDR)

  3. Chemical pneumonitis

    MedlinePlus

    ... fertilizer dust Noxious fumes from pesticides Smoke (from house fires and wildfires) Chronic chemical pneumonitis can occur after only low levels of exposure to the irritant over a long time. This causes inflammation and may lead to ...

  4. Chemical Emergencies

    MedlinePlus

    ... be unintentional, as in the case of an industrial accident. They could also be planned, as in ... and VX. Many hazardous chemicals are used in industry - for example, chlorine, ammonia, and benzene. Some can ...

  5. Chemical Peels

    MedlinePlus

    ... under the eyes and around the mouth). Freckles. Melasma. Rough-feeling skin. Sun-damage skin. Insurance coverage: Chemical peels are considered a cosmetic treatment. Insurance does not cover the cost of cosmetic ...

  6. Chemical sensors

    DOEpatents

    Lowell, Jr., James R.; Edlund, David J.; Friesen, Dwayne T.; Rayfield, George W.

    1992-01-01

    Sensors responsive to small changes in the concentration of chemical species are disclosed, comprising a mechanicochemically responsive polymeric film capable of expansion or contraction in response to a change in its chemical environment, either operatively coupled to a transducer capable of directly converting the expansion or contraction to a measurable electrical or optical response, or adhered to a second inert polymeric strip, or doped with a conductive material.

  7. Chemical sensors

    DOEpatents

    Lowell, J.R. Jr.; Edlund, D.J.; Friesen, D.T.; Rayfield, G.W.

    1992-06-09

    Sensors responsive to small changes in the concentration of chemical species are disclosed, comprising a mechanicochemically responsive polymeric film capable of expansion or contraction in response to a change in its chemical environment, either operatively coupled to a transducer capable of directly converting the expansion or contraction to a measurable electrical or optical response, or adhered to a second inert polymeric strip, or doped with a conductive material. 12 figs.

  8. Chemical sensors

    SciTech Connect

    Hubbard, C.W.; Gordon, R.L.

    1987-05-01

    The revolution in analytical chemistry promised by recent developments in the field of chemical sensors has potential for significant positive impact on both research and production activities conducted by and for the Department of Energy. Analyses which were, in the past, performed only with a roomful of expensive equipment can now be performed with miniature solid-state electronic devices or small optical probes. Progress in the development of chemical sensors has been rapid, and the field is currently growing at a great rate. In accordance, Pacific Northwest Laboratory initiated a survey of recent literature so that contributors to active programs in research on analytical methods could be made aware of principles and applications of this new technology. This report presents the results of that survey. The sensors discussed here are divided into three types: micro solid-state devices, optical sensors, and piezoelectric crystal devices. The report is divided into three corresponding sections. The first section, ''Micro Solid-State Devices,'' discusses the design, operation, and application of electronic sensors that are produced in much the same way as standard solid-state electronic devices. The second section, ''Optrodes,'' covers the design and operation of chemical sensors that use fiber optics to detect chemically induced changes in optical properties. The final section, ''Piezoelectric Crystal Detectors,'' discusses two types of chemical sensors that depend on the changes in the properties of an oscillating piezoelectric crystal to detect the presence of certain materials. Advantages and disadvantages of each type of sensor are summarized in each section.

  9. Chemical networks

    NASA Astrophysics Data System (ADS)

    Thi, Wing-Fai

    2015-09-01

    This chapter discusses the fundamental ideas of how chemical networks are build, their strengths and limitations. The chemical reactions that occur in disks combine the cold phase reactions used to model cold molecular clouds with the hot chemistry applied to planetary atmosphere models. With a general understanding of the different types of reactions that can occur, one can proceed in building a network of chemical reactions and use it to explain the abundance of species seen in disks. One on-going research subject is finding new paths to synthesize species either in the gas-phase or on grain surfaces. Specific formation routes for water or carbon monoxide are discussed in more details. 13th Lecture of the Summer School "Protoplanetary Disks: Theory and Modelling Meet Observations"

  10. Drug laws and the 'derivative' problem.

    PubMed

    King, Leslie A; Ujváry, István; Brandt, Simon D

    2014-01-01

    The concept of a 'derivative' is used widely in chemistry, where its precise meaning depends on the circumstances. However, numerous examples of derivative also occur in domestic drugs legislation, some of which stem from the 1961 United Nations Single Convention on Narcotic Drugs. There is a commonly held view that only 'first-order' derivatives should be considered: substances that can be created from a parent structure in a single chemical reaction. In other words, 'derivatives of derivatives' are excluded. However, some substances related to ecgonine (e.g. 2-carbomethoxytropinone) are clearly convertible to cocaine, even though this may require more than one reaction step. It follows that 2-carbomethoxytropinone is a controlled drug, a situation that most chemists would regard as perverse. A more extreme example of the complexity of 'derivative' is shown by the conversion of thebaine to buprenorphine. Even though this requires six or more stages, the US Drug Enforcement Administration successfully argued in a 1986 case that for the purposes of the Controlled Substances Act, the number of steps required was irrelevant; buprenorphine was a derivative of thebaine. Because the term derivative is rarely defined in statutes, the legal status of some substances, such as 2-bromo-LSD, is uncertain. Although a number of definitions of derivative can be found in the chemical literature, no single definition is adequate to describe all situations where it occurs in legislation. Unless qualified, it is suggested that the term derivative should be avoided in any future legislation. PMID:23949903

  11. Chemical lasers

    NASA Astrophysics Data System (ADS)

    Ablekov, V. K.; Denisov, Iu. N.; Proshkin, V. V.

    1983-08-01

    Recent developments in the theory and application of chemical lasers (CLs) are surveyed in a translation of a book published in Russian in 1980. The laws governing the gas-phase chemical reactions typical of CLs are introduced, the principles of quantum-mechanical description of molecular systems are reviewed, and the kinetics of CL processes are examined. The four general classes of CL are then presented in detail: static-gas, subsonic, supersonic, and detonation CLs. Graphs, diagrams, and drawings of experimental setups are provided.

  12. Chemical releases

    NASA Technical Reports Server (NTRS)

    Heppner, J. P.; Evans, D. S.

    1978-01-01

    A Chemical Release Module to be carried into orbit by the shuttle is described. The module would release chemicals from orbiting satellites in order understand processes within the Earth's magnetosphere, atmosphere and ionosphere. A large number of potential experiments are identified, ranging from introducing traceable material into the solar wind in order to study its transport to and within the magnetosphere, to injecting material into the outer magnetosphere to simulate the precipitation of trapped charged particles, to the release of material at lower altitudes to create waves both mechanical and electromagnetic.

  13. 40 CFR 721.10328 - Salt of polyalkylenepolyamine derivative (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Salt of polyalkylenepolyamine... Specific Chemical Substances § 721.10328 Salt of polyalkylenepolyamine derivative (generic). (a) Chemical... as salt of polyalkylenepolyamine derivative (PMN P-03-530) is subject to reporting under this...

  14. 40 CFR 721.10328 - Salt of polyalkylenepolyamine derivative (generic).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Salt of polyalkylenepolyamine... Specific Chemical Substances § 721.10328 Salt of polyalkylenepolyamine derivative (generic). (a) Chemical... as salt of polyalkylenepolyamine derivative (PMN P-03-530) is subject to reporting under this...

  15. 40 CFR 721.10328 - Salt of polyalkylenepolyamine derivative (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Salt of polyalkylenepolyamine... Specific Chemical Substances § 721.10328 Salt of polyalkylenepolyamine derivative (generic). (a) Chemical... as salt of polyalkylenepolyamine derivative (PMN P-03-530) is subject to reporting under this...

  16. Steaming-induced chemical transformations and holistic quality assessment of red ginseng derived from Panax ginseng by means of HPLC-ESI-MS/MS(n)-based multicomponent quantification fingerprint.

    PubMed

    Xie, Yuan-yuan; Luo, Dan; Cheng, Yi-jun; Ma, Jin-fang; Wang, Yi-ming; Liang, Qiong-lin; Luo, Guo-an

    2012-08-22

    The purpose of this study is to evaluate the steaming-induced chemical transformation of red ginseng manufactured from fresh ginseng by means of simultaneous quantitative and qualitative analyses with a combinative high-performance liquid chromatography-electrospray tandem mass spectrometry (HPLC-ESI-MS/MS(n)) technique. Thirty-six ginsenosides were identified in red ginseng and white ginseng by comparing the mass spectrum and/or matching the empirical molecular formula with that of known published compounds, and 11 of them were determined to be newly generated during the red ginseng preparatory process. The mechanisms involved were further deduced to be hydrolysis, dehydration, isomerization, and decarboxylation at C-20, and hydrolysis also occurs at C-3 or C-6 of the original ginsenosides through the mimic process of steaming and heating in laboratory. The multicomponent quantification fingerprint of ginseng was also established by HPLC-UV method, and the contents of 12 ginsenosides in red and white ginsengs from different sources were determined simultaneously. The ratio of the total content of determined malonyl ginsenosides to the corresponding neutral ginsenosides (T(m-PPD)/T(PPD)) in white ginseng ranged from 0.46 to 0.62 and from 0 to 0.19 in red ginseng. The validated method is expected to provide an effective approach to standardize the processing procedures of ginseng products and regulate the usage of ginseng in Traditional Chinese Medical prescription. PMID:22839102

  17. Synthesis, vapor growth, polymerization, and characterization of thin films of novel diacetylene derivatives of pyrrole. The use of computer modeling to predict chemical and optical properties of these diacetylenes and poly(diacetylenes)

    NASA Technical Reports Server (NTRS)

    Paley, M. S.; Frazier, D. O.; Abeledeyem, H.; Mcmanus, S. P.; Zutaut, S. E.

    1992-01-01

    In the present work two diacetylene derivatives of pyrrole which are predicted by semiempirical AM1 calculations to have very different properties, are synthesized; the polymerizability of these diacetylenes in the solid state is determined, and the results are compared to the computer predictions. Diacetylene 1 is novel in that the monomer is a liquid at room temperature; this may allow for the possibility of polymerization in the liquid state as well as the solid state. Thin poly(diacetylene) films are obtained from compound 1 by growing films of the monomer using vapor deposition and polymerizing with UV light; these films are then characterized. Interestingly, while the poly(diacetylene) from 1 does not possess good nonlinear optical properties, the monomer exhibits very good third-order effects (phase conjugation) in solution. Dilute acetone solutions of the monomer 1 give intensity-dependent refractive indices on the order of 10 exp -6 esu; these are 10 exp 6 times better than for CS2.

  18. Chemical Mahjong

    ERIC Educational Resources Information Center

    Cossairt, Travis J.; Grubbs, W. Tandy

    2011-01-01

    An open-access, Web-based mnemonic game is described whereby introductory chemistry knowledge is tested using mahjong solitaire game play. Several tile sets and board layouts are included that are themed upon different chemical topics. Introductory tile sets can be selected that prompt the player to match element names to symbols and metric

  19. Chemical Indicators.

    ERIC Educational Resources Information Center

    Prombain, Dorothy R.; And Others

    This science sourcebook was written for intermediate grade teachers to provide guidance in teaching a specially developed unit on chemical indicators. Directions and suggestions for guiding student science activities are given. Some of the activities concern soil testing, crystals, and household powders such as sugar and salt. A list of necessary…

  20. Chemical Mahjong

    ERIC Educational Resources Information Center

    Cossairt, Travis J.; Grubbs, W. Tandy

    2011-01-01

    An open-access, Web-based mnemonic game is described whereby introductory chemistry knowledge is tested using mahjong solitaire game play. Several tile sets and board layouts are included that are themed upon different chemical topics. Introductory tile sets can be selected that prompt the player to match element names to symbols and metric…

  1. Delicious Chemicals.

    ERIC Educational Resources Information Center

    Barry, Dana M.

    This paper presents an approach to chemistry and nutrition that focuses on food items that people consider delicious. Information is organized according to three categories of food chemicals that provide energy to the human body: (1) fats and oils; (2) carbohydrates; and (3) proteins. Minerals, vitamins, and additives are also discussed along with…

  2. Chemical Modification of Polysaccharides

    PubMed Central

    Cumpstey, Ian

    2013-01-01

    This review covers methods for modifying the structures of polysaccharides. The introduction of hydrophobic, acidic, basic, or other functionality into polysaccharide structures can alter the properties of materials based on these substances. The development of chemical methods to achieve this aim is an ongoing area of research that is expected to become more important as the emphasis on using renewable starting materials and sustainable processes increases in the future. The methods covered in this review include ester and ether formation using saccharide oxygen nucleophiles, including enzymatic reactions and aspects of regioselectivity; the introduction of heteroatomic nucleophiles into polysaccharide chains; the oxidation of polysaccharides, including oxidative glycol cleavage, chemical oxidation of primary alcohols to carboxylic acids, and enzymatic oxidation of primary alcohols to aldehydes; reactions of uronic-acid-based polysaccharides; nucleophilic reactions of the amines of chitosan; and the formation of unsaturated polysaccharide derivatives. PMID:24151557

  3. Chemical engineering thermodynamics

    SciTech Connect

    Newman, S.A.

    1983-01-01

    This book contains most of the papers presented at the thermodynamics sessions of the Second World Congress of Chemical Engineering held October 4-9, 1981 in Montreal, Canada. The chapters of the book have been categorized into the following areas: (1) Phase Equilibria, (2) Equations of State, (3) Electrolytes, and (4) Other Thermodynamic Topics. Topics presented in the chapters include: thermophysical data banks; group contribution methods applied to phase equilibrai; equations of state for vapor-liquid and liquid-liquid equilibria with applications to design; vapor-liquid equilibria in systems including bitumen, heavy oil and coal-derived liquids; thermodynamics of polar substances; coal char thermochemical data; chemical equilibria; petroleum fraction thermodynamics and sour water vapor-liquid equilibria. (DP)

  4. Measurement and modeling of Ar /H2/CH4 arc jet discharge chemical vapor deposition reactors. I. Intercomparison of derived spatial variations of H atom, C2, and CH radical densities

    NASA Astrophysics Data System (ADS)

    Rennick, C. J.; Ma, J.; Henney, J. J.; Wills, J. B.; Ashfold, M. N. R.; Orr-Ewing, A. J.; Mankelevich, Yu. A.

    2007-09-01

    Comparisons are drawn between spatially resolved absorption spectroscopy data obtained for a 6.4kW dc arc jet reactor, operating with Ar /H2/CH4 gas mixtures, used for deposition of thin, polycrystalline diamond films, and the results of a two-dimensional (r,z) computer model incorporating gas activation, expansion into the low pressure reactor, and the chemistry of the neutral and charged species. The experimental measurements, using either cavity ring-down spectroscopy or diode laser absorption spectroscopy, determined absolute number densities of H(n =2) atoms, and column densities of C2(aΠu3), C2(XΣg+1), and CH(XΠ2) radicals, with vibrational and rotational quantum state resolutions, and their variation with height through the horizontally propagating arc jet plume. Spectra were also analyzed to obtain temperatures and local electron densities [from Stark broadening of H(n =2) absorption lines]. The experimental data are directly compared with the output data of the model that returns spatially inhomogeneous temperature, flow velocities, and number densities of 25 neutral and 14 charged species. Under the base operating conditions of the reactor [11.4SLM (standard liters per minute) of Ar and 1.8SLM of H2 entering the primary torch, with addition of 80SCCM (SCCM denotes cubic centimeter per minute at STP) of CH4 downstream; 6.4kW input power; reactor pressure of 50Torr], the calculated and measured column and number densities agree to within factors of 2-3, the model reproduces the spatial dependence of column densities, and the mean temperatures of C2(a ) and CH(X ) radicals derived from spectra and model results are in good agreement. The model also captures the variation of these parameters with changes to operating conditions of the reactor such as flows of H2 and CH4, and input power. Further details of the model and the insights it provides are the subject of the accompanying paper [Mankelevich et al., J. Appl. Phys. 102, 063310 (2007) ].

  5. Chemical warfare

    PubMed Central

    Samuels, Richard Ian; Mattoso, Thalles Cardoso; Moreira, Denise D.O.

    2013-01-01

    Leaf-cutting ants are well known for their highly complex social organization, which provides them with a strong defense against parasites invading their colonies. Besides this attribute, these insects have morphological, physiological and structural characteristics further reinforcing the defense of their colonies. With the discovery of symbiotic bacteria present on the integument of leaf-cutting ants, a new line of defense was proposed and considered to be specific for the control of a specialized fungal parasite of the ants’ fungus gardens (Escovopsis). However, recent studies have questioned the specificity of the integumental bacteria, as they were also found to inhibit a range of fungi, including entomopathogens. The microbiota associated with the leaf-cutting ant gardens has also been proposed as another level of chemical defense, protecting the garden from parasite invasion. Here we review the chemical defense weaponry deployed by leaf-cutting ants against parasites of their fungus gardens and of the ants themselves. PMID:23795235

  6. CHEMICALS INCORPORATED IN NEST MATERIAL BY RED IMPORTED FIRE ANTS

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Red imported fire ants are believed to incorporate ant-derived chemicals in nesting material. However, only a few chemicals have been identified. One hurdle for such investigation is the interference in chemical analysis from soil-borne chemicals. Ants were found to be able to construct their nes...

  7. Thermodynamic Derivation of the Equilibrium Distribution Functions of Statistical Mechanics.

    ERIC Educational Resources Information Center

    Stoeckly, Beth

    1979-01-01

    Presents a simplified derivation of the equilibrium distribution functions. The derivation proceeds from the change in the Helmholtz free energy when a particle is added to a system of fixed temperature, volume, and chemical potential. The derivations show the relationship between statistical mechanics and macroscopic thermodynamics. (Author/GA)

  8. 40 CFR 721.1760 - Substituted benzotriazole derivatives.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Substituted benzotriazole derivatives... Substances § 721.1760 Substituted benzotriazole derivatives. (a) Chemical substances and significant new uses... derivatives (PMNs P-93-374 and P-93-375) are subject to reporting under this section for the significant...

  9. Combining microbial production with chemical upgrading.

    PubMed

    Goulas, Konstantinos A; Toste, F Dean

    2016-04-01

    This review presents developments in the chemical processing of fermentation-derived compounds, focusing on ethanol, lactic acid, 2,3-butanediol and the acetone-butanol-ethanol mixture. We examine pathways from these products to biologically-derived drop-in fuels, polymers, as well as commodity chemicals, highlighting the role of homogeneous and heterogeneous catalysts in the development of green processes for the production of fuels and high-value-added compounds from biomass. PMID:26773758

  10. Chemical intolerance.

    PubMed

    Dantoft, Thomas M; Andersson, Linus; Nordin, Steven; Skovbjerg, Sine

    2015-01-01

    Chemical intolerance (CI) is a term used to describe a condition in which the sufferer experiences a complex array of recurrent unspecific symptoms attributed to low-level chemical exposure that most people regard as unproblematic. Severe CI constitutes the distinguishing feature of multiple chemical sensitivity (MCS). The symptoms reported by CI subjects are manifold, involving symptoms from multiple organs systems. In severe cases of CI, the condition can cause considerable life-style limitations with severe social, occupational and economic consequences. As no diagnostic tools for CI are available, the presence of the condition can only be established in accordance to criteria definitions. Numerous modes of action have been suggested to explain CI, with the most commonly discussed theories involving the immune system, central nervous system, olfactory and respiratory systems as well as altered metabolic capacity, behavioral conditioning and emotional regulation. However, in spite of more than 50 years of research, there is still a great deal of uncertainties regarding the event(s) and underlying mechanism( s) behind symptom elicitation. As a result, patients are often misdiagnosed or offered health care solutions with limited or no effect, and they experience being met with mistrust and doubt by health care professionals, the social care system and by friends and relatives. Evidence-based treatment options are currently unavailable, however, a person-centered care model based on a multidisciplinary treatment approach and individualized care plans have shown promising results. With this in mind, further research studies and health care solutions should be based on a multifactorial and interdisciplinary approach. PMID:26088215

  11. Chemical durability

    SciTech Connect

    Kreuer, K.D.; Warhus, U.

    1986-03-01

    The chemical durability of NASICON (Na/sub 1+x/Zr/sub 2/Si/sub x/P/sub 3-x/O/sub 12/, x=0-3) versus molten sodium and sulfur at 600 K has been investigated. Degradation by molten sodium has been observed for phosphorus-containing compositions only. The pure silicate (x=3), however, appeared to be stable, because reduction of silicon demanded by thermodynamics did not occur at the given temperature for kinetic reasons. The latter composition has also been shown to have good durability against molten sulfur.

  12. Chemical lasers

    NASA Astrophysics Data System (ADS)

    Khariton, Y.

    1984-08-01

    The application and the advances of quantum electronics, specifically, of optical quantum generators lasers is reviewed. Materials are cut, their surfaces are machined, chemical transformations of substances are carried out, surgical operations are performed, data are transmitted, three dimensional images are produced and the content of microimpurities, in the atmosphere, are analyzed by use of a beam. Laser technology is used in conducting investigations in the most diverse fields of the natural and technical sciences from controlled thermonuclear fusion to genetics. Many demands are placed on lasers as sources of light energy. The importance of low weight, compactness of the optical generator and the efficiency of energy conversion processes is emphasized.

  13. Inflation Rates, Car Devaluation, and Chemical Kinetics.

    ERIC Educational Resources Information Center

    Pogliani, Lionello; Berberan-Santos, Mario N.

    1996-01-01

    Describes the inflation rate problem and offers an interesting analogy with chemical kinetics. Presents and solves the car devaluation problem as a normal chemical kinetic problem where the order of the rate law and the value of the rate constant are derived. (JRH)

  14. Phenolic Derivatives from Hypericum japonicum.

    PubMed

    Luo, Guoyong; Zhou, Min; Ye, Qi; Mi, Jun; Fang, Dongmei; Zhang, Guolin; Luo, Yinggang

    2015-12-01

    Three new acylphloroglucinol glycosides, hypericumols A - C, together with fifteen known phenolic derivatives, were isolated from the total phenolic extract of Hypericum japonicum. Hypericumols A, B, and C were characterized as 4,6-dimethyl-2-methylpropanoylphloroglucinol-1-O-β-D-glucopyranoside (1), 4-methyl-2-methylpropanoylphloroglucinol-1-O-β-D-glucopyranoside (2), and (2'S)-4,6-dimethyl-2-methylbutyrylphloroglucinol-1-O-β-D-glucopyranoside (3), respectively, on the basis of spectroscopic data interpretation and chemical degradation reaction. PMID:26882677

  15. Chemical Analyses

    NASA Technical Reports Server (NTRS)

    Bulluck, J. W.; Rushing, R. A.

    1994-01-01

    As a preliminary study on the effects of chemical aging of polymer materials MERL and TRI have examined two polymeric materials that are typically used for offshore umbilical applications. These two materials were Tefzel, a copolymer of ethylene and tetrafluoroethylene, and Coflon, polyvinylidene fluoride. The Coflon specimens were cut from pipe sections and exposed to H2S at various temperatures and pressures. One of these specimens was tested for methane permeation, and another for H2S permeation. The Tefzel specimens were cut from .05 mm sheet stock material and were exposed to methanol at elevated temperature and pressure. One of these specimens was exposed to methanol permeation for 2 days at 100 C and 2500 psi. An additional specimen was exposed to liquid methanol for 3 days at 150 C and 15 Bar. Virgin specimens of each material were similarly prepared and tested.

  16. Household Chemical Emergencies

    MedlinePlus

    ... Hazardous Materials Incidents Household Chemical Emergencies Nuclear Power Plants Main Content Household Chemical Emergencies Nearly every household uses products containing hazardous materials or chemicals. Although the ...

  17. Effects of metformin, buformin, and phenformin on the post-initiation stage of chemically induced mammary carcinogenesis in the rat.

    PubMed

    Zhu, Zongjian; Jiang, Weiqin; Thompson, Matthew D; Echeverria, Dimas; McGinley, John N; Thompson, Henry J

    2015-06-01

    Metformin is a widely prescribed drug for the treatment of type II diabetes. Although epidemiologic data have provided a strong rationale for investigating the potential of this biguanide for use in cancer prevention and control, uncertainty exists whether metformin should be expected to have an impact in nondiabetic patients. Furthermore, little attention has been given to the possibility that other biguanides may have anticancer activity. In this study, the effects of clinically relevant doses of metformin (9.3 mmol/kg diet), buformin (7.6 mmol/kg diet), and phenformin (5.0 mmol/kg diet) were compared with rats fed control diet (AIN93-G) during the post-initiation stage of 1-methyl-1-nitrosourea-induced (50 mg/kg body weight) mammary carcinogenesis (n = 30/group). Plasma, liver, skeletal muscle, visceral fat, mammary gland, and mammary carcinoma concentrations of the biguanides were determined. In comparison with the control group, buformin decreased cancer incidence, multiplicity, and burden, whereas metformin and phenformin had no statistically significant effect on the carcinogenic process relative to the control group. Buformin did not alter fasting plasma glucose or insulin. Within mammary carcinomas, evidence was obtained that buformin treatment perturbed signaling pathways related to energy sensing. However, further investigation is needed to determine the relative contributions of host systemic and cell autonomous mechanisms to the anticancer activity of biguanides such as buformin. PMID:25804611

  18. ARIANE 5 light derivatives

    NASA Astrophysics Data System (ADS)

    Astorg, Jean-Marc

    1993-01-01

    The Ariane 5 light derivatives are studied in order to complete Ariane 5 launch services with regard to medium size Sun synchronous spacecrafts (S derivative) and small satellites (P derivative). The P derivative is a three stage launcher with two solid propellant motors and a bipropellant upper stage. It is capable of placing 1 ton in a 1000 km circular polar orbit or two 450 kg payloads in the same orbit. The light derivatives are mainly derived from the Ariane 5 solid propellant booster and upper stage. The payload volume is particulary large (2.8 m internal maximal diameter, 6 m height). The light derivatives will be launched from the Ariane spaceport in Guyana. They will use Ariane 5 facilities for payload preparation and launch operation with a specific building for launcher integration. The first flight of the P derivative is scheduled for 1998.

  19. Potassium niobate derived from a novel chemical solution

    NASA Astrophysics Data System (ADS)

    Cheng, Z. X.; Ozawa, K.; Miyazaki, A.; Kimura, H.

    2005-02-01

    Potassium niobate (KNbO 3) were successfully prepared by the solution processing through the reaction of aqueous H 2O 2 solution with niobium and potassium alkoxides. In this process, potassium and niobate peroxide formed as the precursor for KNbO 3. Precursor powder crystallized into KNbO 3 at a sintering temperature as low as 650 °C in oxygen. KNbO 3 thin films comprised of uniform grains with dimension of around 100 nm were fabricated.

  20. Physical and chemical characterization of waste wood derived biochars

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Biochar, a solid byproduct generated during waste biomass pyrolysis or gasification in the absence (or near-absence) of oxygen, has recently garnered interest for both agricultural and environmental management purposes owing to its unique physicochemical properties, such as its high surface area and...

  1. Quantum-chemical evaluation of basicity of acridine derivatives

    SciTech Connect

    Pedash, V.F.; Gaidukevich, A.N.

    1986-08-01

    It has been found that the antibacterial effect of aminoacridines increases with the increase of the degree of their cationic ionization, while changes in the structure are relatively minor as concern the activity. The authors study the possible determination of a dependence between the pK of monosubstituted acridines on the position of substituent in their molecules. The theory of perturbations of molecular orbitals in its simplest variation was used. A comparison is shown of theoretical and experimental data on pK of monoaminoacridines.

  2. Distillation of natural fatty acids and their chemical derivatives

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Well over 1,000 different fatty acids are known which are natural components of fats, oils (triacylglycerols), and other related compounds. These fatty acids can have different alkyl chain lengths, 0-6 carbon-carbon double bonds possessing cis- or trans-geometry, and can contain a variety of functio...

  3. Chemical factors affecting insolubles formation in shale derived diesel fuel

    SciTech Connect

    Beal, E.J.; Mushrush, G.W.; Cooney, J.V. ); Watkins, J.M. )

    1989-01-01

    Detrimental changes in fuel properties with time have been a continuing problem in the use of middle distillate fuels. Instability of diesel fuels is usually defined by the formation of insoluble sediments and gums. Gravimetric stability tests have been conducted at 43/sup 0/ and 80/sup 0/C, respectively, using three model nitrogen heterocycles, 2-methylpyridine, 2,6-di methyl quinoline, and dodecahydrocarbazole, as dopants in an otherwise stable shale diesel fuel. Potential interactive effects have been defined for these three model nitrogen heterocycles in the stable fuel in the presence of a second model dopant, t-butyl hydroperoxide. 2-Methyl pyridine and 2,6-dimethyl quinoline were inactive and only 2-methyl pyridine showed slight positive interactive effects. Dodecahydrocarbazole formed large amounts of insolubles by itself and exhibited positive interactive effects.

  4. Quantum chemical assessment of benzimidazole derivatives as corrosion inhibitors

    PubMed Central

    2014-01-01

    Background The majority of well-known inhibitors are organic compounds containing multiple bonds and heteroatoms, such as O, N or S, which allow adsorption onto the metal surface. These compounds can adsorb onto the metal surface and block active surface sites, reducing the rate of corrosion. Results A comparative theoretical study of three benzimidazole isomers, benzimidazole (BI), 2-methylbenzimidazole (2-CH3-BI), and 2-mercaptobenzimidazole (2-SH-BI), as corrosion inhibitors was performed using density functional theory (DFT) with the B3LYP functional basis set. Conclusions Nitro and amino groups were selected for investigation as substituents of the three corrosion inhibitors. Nitration of the corrosion inhibitor molecules led to a decrease in inhibition efficiency, while reduction of the nitro group led to an increase in inhibition efficiency. These aminobenzimidazole isomers represent a significant improvement in the inhibition efficiency of corrosion inhibitor molecules. PMID:24674343

  5. Chemical reactivity and intracavitary application of alkylating sugar alcohol derivatives.

    PubMed

    Kerpel-Fronius, S; Csetényi, J; Hegedüs, L; Horváth, I P; Ringwald, G; Töttössy, B; Eckhardt, S

    1980-01-01

    Lycurium [1,4-di-(methylsulfonyloxy-ethylamino)-1,4-didesoxy-erythrioldimethylsulfonate; R-74; NSC-122402] undergoes rapid hydrolysis in aqueous solutions. The concentration of the alkylating compound(s), demonstrated by the 4-(4'-nitrobenzyl)pyridine reaction, decreases approximately by 80% in 10 min following the dissolution of the drug in saline. In patients peak plasma concentration of radioactivity after the intracavitary injection of 14C-labelled Lycurim is observed between 4 and 6 h. It is assumed, therefore, that only a negligible amount of pharmacologically active alkylating compounds reaches the circulation after intracavitary application. This conclusion is supported by clinical experience showing that intracavitary administration of the same amount of Lycurim causes much milder systemic side-effects than intravenous injection. A dose escalation study was started to determine the applicability of Lycurim in the form of high volume intraperitoneal instillation ('belly bath') for the treatment of ovarian cancer. PMID:6893858

  6. 40 CFR 721.10147 - Acrylate derivative of alkoxysilylalkane ester and mixed metal oxides (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Acrylate derivative of... SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.10147 Acrylate derivative of... reporting. (1) The chemical substance identified generically as acrylate derivative of...

  7. 40 CFR 721.10148 - Acryloxy alkanoic alkane derivative with mixed metal oxides (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Acryloxy alkanoic alkane derivative... Significant New Uses for Specific Chemical Substances § 721.10148 Acryloxy alkanoic alkane derivative with...) The chemical substance identified generically as acryloxy alkanoic alkane derivative with mixed...

  8. 40 CFR 721.4520 - Isopropylidene, bis(1,1-dimethylpropyl) derivative.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ...) derivative. 721.4520 Section 721.4520 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED... Specific Chemical Substances § 721.4520 Isopropylidene, bis(1,1-dimethylpropyl) derivative. (a) Chemical... isopropylidene, bis(1,1-dimethylpropyl) derivative (PMN P-85-648) is subject to reporting under this section...

  9. 40 CFR 721.558 - Salt of a fatty alkylamine derivative (generic).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Salt of a fatty alkylamine derivative... Specific Chemical Substances § 721.558 Salt of a fatty alkylamine derivative (generic). (a) Chemical... as a salt of a fatty alkylamine derivative (PMN P-96-1426) is subject to reporting under this...

  10. 40 CFR 721.558 - Salt of a fatty alkylamine derivative (generic).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Salt of a fatty alkylamine derivative... Specific Chemical Substances § 721.558 Salt of a fatty alkylamine derivative (generic). (a) Chemical... as a salt of a fatty alkylamine derivative (PMN P-96-1426) is subject to reporting under this...

  11. 40 CFR 721.558 - Salt of a fatty alkylamine derivative (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Salt of a fatty alkylamine derivative... Specific Chemical Substances § 721.558 Salt of a fatty alkylamine derivative (generic). (a) Chemical... as a salt of a fatty alkylamine derivative (PMN P-96-1426) is subject to reporting under this...

  12. 40 CFR 721.558 - Salt of a fatty alkylamine derivative (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Salt of a fatty alkylamine derivative... Specific Chemical Substances § 721.558 Salt of a fatty alkylamine derivative (generic). (a) Chemical... as a salt of a fatty alkylamine derivative (PMN P-96-1426) is subject to reporting under this...

  13. Deriving Verbs in English

    ERIC Educational Resources Information Center

    Dixon, R. M. W.

    2008-01-01

    Phonological and semantic principles which underlie the derivation of verbs from nouns and adjectives in English are examined. There is intricate phonological conditioning for suffix "-ize" and for suffix "-(i)fy"; a third major process is zero derivation. These derivational processes cover more than a score of semantic relations (some with…

  14. Deriving Verbs in English

    ERIC Educational Resources Information Center

    Dixon, R. M. W.

    2008-01-01

    Phonological and semantic principles which underlie the derivation of verbs from nouns and adjectives in English are examined. There is intricate phonological conditioning for suffix "-ize" and for suffix "-(i)fy"; a third major process is zero derivation. These derivational processes cover more than a score of semantic relations (some with

  15. Nonlinear response theory in chemical kinetics

    PubMed Central

    Kryvohuz, Maksym; Mukamel, Shaul

    2014-01-01

    A theory of nonlinear response of chemical kinetics, in which multiple perturbations are used to probe the time evolution of nonlinear chemical systems, is developed. Expressions for nonlinear chemical response functions and susceptibilities, which can serve as multidimensional measures of the kinetic pathways and rates, are derived. A new class of multidimensional measures that combine multiple perturbations and measurements is also introduced. Nonlinear fluctuation-dissipation relations for steady-state chemical systems, which replace operations of concentration measurement and perturbations, are proposed. Several applications to the analysis of complex reaction mechanisms are provided. PMID:25669367

  16. ASSESSING BIOACCUMULATION FOR DERIVING NATIONAL HUMAN HEALTH WATER QUALITY CRITERIA

    EPA Science Inventory

    The United States Environmental Protection Agency is revising its methodology for deriving national ambient water quality criteria (AWQC) to protect human health. A component of this guidance involves assessing the potential for chemical bioaccumulation in commonly consumed fish ...

  17. Haenamindole, an unusual diketopiperazine derivative from a marine-derived Penicillium sp. KCB12F005.

    PubMed

    Kim, Jong Won; Ko, Sung-Kyun; Son, Sangkeun; Shin, Kee-Sun; Ryoo, In-Ja; Hong, Young-Soo; Oh, Hyuncheol; Hwang, Bang Yeon; Hirota, Hiroshi; Takahashi, Shunji; Kim, Bo Yeon; Osada, Hiroyuki; Jang, Jae-Hyuk; Ahn, Jong Seog

    2015-11-15

    During the chemical investigation of marine-derived fungus, an unusual diketopiperazine (DKP) alkaloid, haenamindole (1), was isolated from a culture of the marine-derived fungus Penicillium sp. KCB12F005. The structure of 1, which possesses benzyl-hydroxypiperazindione and phenyl-pyrimidoindole rings system in the molecule, was elucidated by analysis of NMR and MS data. The stereochemistry of 1 was determined by ROESY and advanced Marfey's method. PMID:26403931

  18. [Chemical food contaminants].

    PubMed

    Schrenk, D

    2004-09-01

    Chemical food contaminants are substances which are neither present naturally in the usual raw material used for food production nor are added during the regular production process. Examples are environmental pollutants or contaminants derived from agricultural production of crops or livestock or from inadequate manufacturing of the food product itself. More difficult is the classification of those compounds formed during regular manufacturing such as products of thermal processes including flavoring substances. In these cases, it is common practice to call those compounds contaminants which are known for their adverse effects such as acrylamide, whereas constituents which add to the food-specific flavor such as Maillard products formed during roasting, baking etc. are not termed contaminants. From a toxicological viewpoint this distinction is not always clear-cut. Important groups of chemical contaminants are metals such as mercury or lead, persistent organic pollutants such as polychlorinated biphenyls and related pollutants, which are regularly found in certain types of food originating from background levels of these compounds in our environment. Furthermore, natural toxins form microorganisms or plants, and compounds formed during thermal treatment of food are of major interest. In general, a scientific risk assessment has to be carried out for any known contaminant. This comprises an exposure analysis and a toxicological and epidemiological assessment. On these grounds, regulatory and/or technological measures can often improve the situation. Major conditions for a scientific risk assessment and a successful implementation of regulations are highly developed food quality control, food toxicology and nutritional epidemiology. PMID:15378171

  19. The Chemical Potential

    NASA Astrophysics Data System (ADS)

    Kaplan, Thomas

    2005-03-01

    The definition of the fundamental quantity, the chemical potential (c.p.), is confused in the literature, there being at least three distinct definitions in various books and papers. Major differences among them can occur for finite systems. We resolve the situation by arguing that the chemical potential defined by the symbol μ conventionally appearing in the grand canonical density operator is the uniquely correct definition, the grand canonical ensemble being the only one of the various ensembles usually discussed (microcanonical, canonical, Gibbs, grand canonical) that is appropriate for statistical thermodynamics, whenever the c.p. is physically relevant. The derivation of the zero-temperature limit of this μ for rather general interacting-electron systems by Perdew et. al.,[1] is discussed and extended. The enormous finite-size corrections (in systems >> a cm^3) for one rather common definition of the c.p., found by Shegelski [2] within the standard effective mass model of an ideal intrinsic semiconductor, are discussed. The quantum dot is mentioned as a small-system application. 1. J. F. Perdew et. al., Phys. Rev. Lett. 23, 1691 (1982); J. F. Perdew, in Density-functional methods in Physics, edited by R. M. Dreizler and J. da Providencia, Plenum Press, 1985. 2. M. R. A. Shegelski, Solid State Commun. 38, 351 (1986); Am. J. Phys. 72, 676 (2004).

  20. Endohedral Metallofullerene Derivatives

    NASA Technical Reports Server (NTRS)

    Dorn, Harry C. (Inventor); Iezzi, Erick B. (Inventor); Duchamp, James (Inventor)

    2008-01-01

    Trimetallic nitride endohedral metallofullerene derivatives and their preparation are described. The trimetallic nitride endohedral metallofullerene derivatives have the general formula A(sub 3-n)X(sub n)@C(sub m)(R) where n ranges from 0 to 3, A and X may be trivalent metals and may be either rare earth metal or group IIIB metals, m is between about 60 and about 200, and R is preferably an organic group. Derivatives where the R group forms cyclized derivatives with the fullerene cage are also described.

  1. Cytotoxic dibromotyrosine-derived metabolites from the sponge Aplysina gerardogreeni.

    PubMed

    Hernndez-Guerrero, Claudia J; Zuba, Eva; Ortega, Mara J; Carballo, J Luis

    2007-08-01

    The chemical study of the sponge Aplysina gerardogreeni collected at the Gulf of California has led to the isolation of four new dibromotyrosine-derived metabolites, aplysinones A-D, whose structures were determined by spectroscopic analysis and chemical methods. The new compounds and four semisynthetic analogues prepared in this study have shown cytotoxic activity against human tumor cell lines. PMID:17512741

  2. 40 CFR 721.9740 - Brominated triazine derivative.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Brominated triazine derivative. 721.9740 Section 721.9740 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.9740 Brominated...

  3. Chemical Ecology: Chemical Communication in Nature.

    ERIC Educational Resources Information Center

    Wood, William F.

    1983-01-01

    Substances that deliver chemical messages between same/different species are called semiochemicals. Surveyed are three types of semiochemicals (pheromones, allomones, and kairomones), types of organisms involved, and specific chemicals used to carry the various kinds of messages. (JN)

  4. Azaphilone and Diphenyl Ether Derivatives from a Gorgonian-Derived Strain of the Fungus Penicillium pinophilum.

    PubMed

    Zhao, Dong-Lin; Shao, Chang-Lun; Zhang, Qiang; Wang, Kai-Ling; Guan, Fei-Fei; Shi, Ting; Wang, Chang-Yun

    2015-09-25

    Three new azaphilone derivatives, pinophilins D-F (1-3), and one new diphenyl ether derivative, hydroxypenicillide (10), together with nine known compounds (4-9, 11-13), were isolated from the gorgonian-derived fungus Penicillium pinophilum XS-20090E18. Their structures including absolute configurations were determined by spectroscopic data, chemical conversions, the ECD exciton chirality method, and ECD calculations. Compounds 10-13 exhibited inhibitory activity against the larval settlement of the barnacle Balanus amphitrite at nontoxic concentrations. Compounds 10 and 11 showed cytotoxicity against Hep-2, RD, and HeLa cell lines. PMID:26291474

  5. Renewable Chemicals: Dehydroxylation of Glycerol and Polyols

    PubMed Central

    ten Dam, Jeroen; Hanefeld, Ulf

    2011-01-01

    The production of renewable chemicals is gaining attention over the past few years. The natural resources from which they can be derived in a sustainable way are most abundant in sugars, cellulose and hemicellulose. These highly functionalized molecules need to be de-functionalized in order to be feedstocks for the chemical industry. A fundamentally different approach to chemistry thus becomes necessary, since the traditionally employed oil-based chemicals normally lack functionality. This new chemical toolbox needs to be designed to guarantee the demands of future generations at a reasonable price. The surplus of functionality in sugars and glycerol consists of alcohol groups. To yield suitable renewable chemicals these natural products need to be defunctionalized by means of dehydroxylation. Here we review the possible approaches and evaluate them from a fundamental chemical aspect. PMID:21887771

  6. 40 CFR 721.646 - Aminofluoran derivative (generic name).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Aminofluoran derivative (generic name). 721.646 Section 721.646 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC... Substances § 721.646 Aminofluoran derivative (generic name). (a) Chemical substance and significant new...

  7. 40 CFR 721.646 - Aminofluoran derivative (generic name).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Aminofluoran derivative (generic name). 721.646 Section 721.646 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC... Substances § 721.646 Aminofluoran derivative (generic name). (a) Chemical substance and significant new...

  8. 40 CFR 721.646 - Aminofluoran derivative (generic name).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Aminofluoran derivative (generic name). 721.646 Section 721.646 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC... Substances § 721.646 Aminofluoran derivative (generic name). (a) Chemical substance and significant new...

  9. 40 CFR 721.646 - Aminofluoran derivative (generic name).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Aminofluoran derivative (generic name). 721.646 Section 721.646 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC... Substances § 721.646 Aminofluoran derivative (generic name). (a) Chemical substance and significant new...

  10. Scaling up of renewable chemicals.

    PubMed

    Sanford, Karl; Chotani, Gopal; Danielson, Nathan; Zahn, James A

    2016-04-01

    The transition of promising technologies for production of renewable chemicals from a laboratory scale to commercial scale is often difficult and expensive. As a result the timeframe estimated for commercialization is typically underestimated resulting in much slower penetration of these promising new methods and products into the chemical industries. The theme of 'sugar is the next oil' connects biological, chemical, and thermochemical conversions of renewable feedstocks to products that are drop-in replacements for petroleum derived chemicals or are new to market chemicals/materials. The latter typically offer a functionality advantage and can command higher prices that result in less severe scale-up challenges. However, for drop-in replacements, price is of paramount importance and competitive capital and operating expenditures are a prerequisite for success. Hence, scale-up of relevant technologies must be interfaced with effective and efficient management of both cell and steel factories. Details involved in all aspects of manufacturing, such as utilities, sterility, product recovery and purification, regulatory requirements, and emissions must be managed successfully. PMID:26874264

  11. Terpenes from Marine-Derived Fungi

    PubMed Central

    Ebel, Rainer

    2010-01-01

    Terpenes from marine-derived fungi show a pronounced degree of structural diversity, and due to their interesting biological and pharmacological properties many of them have aroused interest from synthetic chemists and the pharmaceutical industry alike. The aim of this paper is to give an overview of the structural diversity of terpenes from marine-derived fungi, highlighting individual examples of chemical structures and placing them in a context of other terpenes of fungal origin. Wherever possible, information regarding the biological activity is presented. PMID:20948911

  12. CHEMICAL SAFETY ALERTS-

    EPA Science Inventory

    Chemical Safety Alerts are short publications which explain specific hazards that have become evident through chemical accident investigation efforts. EPA has produced over a dozen Alerts to date. This year's Alert: Managing Chemical Reactivity Hazards

  13. CHEMICALS IN PROGRESS BULLETIN

    EPA Science Inventory

    Chemicals in Progress Bulletin is a quarterly newsletter which highlights regulatory and program activities of the Office of Pollution Prevention and Toxics. Regular features and news items include the existing chemicals program, new chemicals program, pollution prevention activi...

  14. Microfluidic chemical reaction circuits

    DOEpatents

    Lee, Chung-cheng; Sui, Guodong; Elizarov, Arkadij; Kolb, Hartmuth C.; Huang, Jiang; Heath, James R.; Phelps, Michael E.; Quake, Stephen R.; Tseng, Hsian-rong; Wyatt, Paul; Daridon, Antoine

    2012-06-26

    New microfluidic devices, useful for carrying out chemical reactions, are provided. The devices are adapted for on-chip solvent exchange, chemical processes requiring multiple chemical reactions, and rapid concentration of reagents.

  15. Chemical Emergencies Overview

    MedlinePlus

    ... might be possible for terrorists to get these chemical warfare agents and use them to harm people. Many ... and disposal of contaminated clothing . Basic information on chemical emergencies Basic chemical emergency information designed for the public ...

  16. Nature's chemicals and synthetic chemicals: Comparative toxicology

    SciTech Connect

    Ames, B.N.; Profet, M.; Gold, L.S. )

    1990-10-01

    The toxicology of synthetic chemicals is compared to that of natural chemicals, which represent the vast bulk of the chemicals to which humans are exposed. It is argued that animals have a broad array of inducible general defenses to combat the changing array of toxic chemicals in plant food (nature's pesticides) and that these defenses are effective against both natural and synthetic toxins. Synthetic toxins such as dioxin are compared to natural chemicals, such as indole carbinol (in broccoli) and ethanol. Trade-offs between synthetic and natural pesticides are discussed. The finding that in high-dose tests, a high proportion of both natural and synthetic chemicals are carcinogens, mutagens, teratogens, and clastogens (30-50{percent} for each group) undermines current regulatory efforts to protect public health from synthetic chemicals based on these tests.

  17. Exposure Levels for Chemical Threat Compounds; Information to Facilitate Chemical Incident Response

    SciTech Connect

    Hauschild, Veronique; Watson, Annetta Paule

    2013-01-01

    Exposure Standards, Limits and Guidelines for Chemical Threat Compunds ABSTRACT Exposure criteria for chemical warfare (CW) agents and certain toxic industrial chemicals (TICs) used as CW agents (such as chlorine fill in an improvised explosive device) have been developed for protection of the civilian general public, civilian employees in chemical agent processing facilities and deployed military populations. In addition, compound-specific concentrations have been developed to serve as how clean is clean enough clearance criteria guiding facility recovery following chemical terrorist or other hazardous release events. Such criteria are also useful to verify compound absence, identify containment boundaries and expedite facility recovery following chemical threat release. There is no single right value or concentration appropriate for all chemical hazard control applications. It is acknowledged that locating and comparing the many sources of CW agent and TIC exposure criteria has not been previously well-defined. This paper summarizes many of these estimates and assembles critical documentation regarding their derivation and use.

  18. Chemical Management System

    Energy Science and Technology Software Center (ESTSC)

    1998-10-30

    CMS provides an inventory of all chemicals on order or being held in the laboratory, to provide a specific location for all chemical containers, to ensure that health and safety regulatory codes are being upheld, and to provide PNNL staff with hazardous chemical information to better manage their inventories. CMS is comprised of five major modules: 1) chemical purchasing, 2) chemical inventory, 3) chemical names, properties, and hazard groups, 4) reporting, and 5) system administration.

  19. Chemical Growth Regulators for Guayule Plants

    NASA Technical Reports Server (NTRS)

    Dastoor, M. N.; Schubert, W. W.; Petersen, G. R.

    1982-01-01

    Test Tubes containing Guayule - tissue cultures were used in experiments to test effects of chemical-growth regulators. The shoots grew in response to addition of 2-(3,4-dichlorophenoxy)-triethylamine (triethylamine (TEA) derivative) to agar medium. Preliminary results indicate that a class of compounds that promotes growth in soil may also promote growth in a culture medium. Further experiments are needed to define the effect of the TEA derivative.

  20. Chemical evolution models for NGC 6822 using planetary nebulae abundances

    NASA Astrophysics Data System (ADS)

    Hernández-Martínez, Liliana; Carigi, Leticia; Peña, Miriam; Peimbert, Manuel

    2012-08-01

    We present chemical evolution models for the dwarf irregular NGC 6822, using chemical abundances of Planetary Nebulae (PNe) and HII regions and also the mass of gas (M gas ) as observational constraints. Chemical evolution models have been calculated to reproduce the abundances as derived from both, collisionally excited lines (CELs) and recombination lines (RLs). In our models, the chemical contribution of low and intermediate mass stars (LIMS) is time delayed, while for the massive stars the chemical contribution is instantaneous, as in Franco & Carigi (2008). The chemical contribution of SNIa is included in our model, thus we are also able to reproduce the observational Fe/H abundance obtained from A stars.

  1. The azobenzene derivatives

    NASA Astrophysics Data System (ADS)

    Ionita, Ionica; Radulescu, Cristiana; Poinescu, Aurora Anca; Anghelina, Florina Violeta; Bunghez, Raluca; Ion, Rodica-Mariana

    2015-02-01

    Azobenzene derivatives constitute a group of dyes which have photochromic properties and have been investigated as promising systems for diverse applications in the unconventional optic area, their properties can be moulded with help of light.

  2. Teaching Cournot without Derivatives.

    ERIC Educational Resources Information Center

    Dufwenberg, Martin

    2001-01-01

    Presents a simple technique for teaching the Cournot model to first-year microeconomic students. Involves demonstrating, without the use of derivatives, that out of all rectangles with a common perimeter, the square has the greatest area. (RLH)

  3. Chemical Education in Europe.

    ERIC Educational Resources Information Center

    Farago, P. J., Ed.; And Others

    This book is a result of a project sponsored by the Working Party on Chemical Education of the Federation of European Chemical Societies, UNESCO, the Chemical Society and the Royal Society, London, England. The purposes of this publication are to: (1) inform chemists of the level and significance of the various chemical qualifications in Europe;…

  4. 40 CFR 721.10321 - Bis[phenyl, 2H-1,3-benzoxazine]derivative (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Bis derivative (generic). 721.10321... Substances § 721.10321 Bis derivative (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as bis derivative (PMN P-03-194) is subject...

  5. 40 CFR 721.10539 - Bis[phenyl-2H-1,3-benzoxazine]derivative (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Bis derivative (generic). 721.10539... Substances § 721.10539 Bis derivative (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as bis derivative (PMN P-02-653) is subject...

  6. 40 CFR 721.10321 - Bis[phenyl, 2H-1,3-benzoxazine]derivative (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Bis derivative (generic). 721.10321... Substances § 721.10321 Bis derivative (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as bis derivative (PMN P-03-194) is subject...

  7. 40 CFR 721.10321 - Bis[phenyl, 2H-1,3-benzoxazine]derivative (generic).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Bis derivative (generic). 721.10321... Substances § 721.10321 Bis derivative (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as bis derivative (PMN P-03-194) is subject...

  8. 40 CFR 721.10539 - Bis[phenyl-2H-1,3-benzoxazine]derivative (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Bis derivative (generic). 721.10539... Substances § 721.10539 Bis derivative (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as bis derivative (PMN P-02-653) is subject...

  9. 40 CFR 721.1300 - [(Dinitrophenyl)azo]-[2,4-dia-mino-5-methoxybenzene] derivatives.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false - derivatives. 721.1300 Section 721... - derivatives. (a) Chemical substances and significant new uses subject to reporting. (1) The chemical substances identified generically as - derivatives (P-83-817 and P-83-818) are subject to reporting...

  10. 40 CFR 721.9078 - 6-Methoxy-1H-benz[de]isoquinoline-2 [3H]-dione derivative (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... -dione derivative (generic). 721.9078 Section 721.9078 Protection of Environment ENVIRONMENTAL PROTECTION... derivative (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as 6-methoxy-1H-benz isoquinoline-2 -dione derivative (PMN P-00-1205)...

  11. PINS chemical identification software

    DOEpatents

    Caffrey, Augustine J.; Krebs, Kennth M.

    2004-09-14

    An apparatus and method for identifying a chemical compound. A neutron source delivers neutrons into the chemical compound. The nuclei of chemical elements constituting the chemical compound emit gamma rays upon interaction with the neutrons. The gamma rays are characteristic of the chemical elements constituting the chemical compound. A spectrum of the gamma rays is generated having a detection count and an energy scale. The energy scale is calibrated by comparing peaks in the spectrum to energies of pre-selected chemical elements in the spectrum. A least-squares fit completes the calibration. The chemical elements constituting the chemical compound can be readily determined, which then allows for identification of the chemical compound.

  12. Dielectric transition of polyacrylonitrile derived carbon nanofibers

    NASA Astrophysics Data System (ADS)

    Li, Jiangling; Su, Shi; Zhou, Lei; Abbot, Andrew M.; Ye, Haitao

    2014-09-01

    The dielectric behavior of polyacrylonitrile derived carbon nanofibers formed at different carbonization temperatures was investigated using impedance spectroscopy. The impedance data are presented in the form of Cole-Cole plots and four equivalent electrical circuits are derived. It is found that by increasing carbonization temperature from 500 to 800 °C, a strong capacitive element in the parallel equivalent circuit is transformed into an inductive element, while the contact resistance and parallel resistance are significantly decreased. Along with the morphological and chemical structural evolution, respectively witnessed by scanning electron microscopy and Raman spectroscopy, the dielectric transition deduced from the transformation of electrical circuits can be correlated to the proposed microstructural changes of polyacrylonitrile derived carbon nanofibers and the interaction/interference among them.

  13. Beyond new chemical entities

    PubMed Central

    Caoili, Salvador Eugenio C; Caoili, Salvador Eugenio C

    2014-01-01

    Antibody-type agents (i.e., antibodies and derivatives thereof) may be produced as clinically valuable antidotes, which conceivably could be developed in tandem with prospective new pharmaceutical products so as to render the risks of clinical trials more acceptable from a regulatory standpoint. Yet, this is but a relatively narrow view of the full potential utility associated with antibody-type agents, the significance of which is appreciated upon reconsidering key aspects of early modern biomedical research (notably major contributions thereto by Nobel Laureate Paul Ehrlich) in light of much more recent advances (e.g., application of immunity-oriented approaches to diseases in general, epitope-specific targeting, abzyme-mediated catalysis, antibody-mediated sustained-release buffering of unbound-ligand concentrations, and enhanced thermal and metabolic stability of deuterated chemical species via the kinetic isotope effect), as conditioned by health-related concerns (e.g., current and anticipated epidemiologic transitions vis-a-vis environmental changes) especially with regard to sustainable development (e.g., emphasizing more efficient resource utilization toward increased global resilience based on greater independence from high-maintenance technological infrastructure). The broader view that thus emerges highlights the urgent need to rebalance the health-research agenda, which presently reflect an overemphasis on small-molecule candidate-drug discovery, in order to advance health based on a comprehensive fundamental synthesis of immunity and pharmacology. PMID:24632567

  14. CHEMICAL SYNTHESIS OF GLYCOSYLPHOSPHATIDYLINOSITOL ANCHORS

    PubMed Central

    Swarts, Benjamin M.; Guo, Zhongwu

    2013-01-01

    Many eukaryotic cell-surface proteins and glycoproteins are anchored to the plasma membrane by glycosylphosphatidylinositols (GPIs), a family of glycolipids that are post-translationally attached to proteins at their C-termini. GPIs and GPI-anchored proteins play important roles in many biological and pathological events, such as cell recognition and adhesion, signal transduction, host defense, and acting as receptors for viruses and toxins. Chemical synthesis of structurally defined GPI anchors and GPI derivatives is a necessary step toward understanding the properties and functions of these molecules in biological systems and exploring their potential therapeutic applications. In the first part of this comprehensive article on the chemical synthesis of GPIs, classic syntheses of naturally occurring GPI anchors from protozoan parasites, yeast, and mammals are covered. The second part of the article focuses on recent diversity-oriented strategies for the synthesis of GPI anchors containing unsaturated lipids, “click chemistry” tags, and highly branched and modified structures. PMID:22794184

  15. Olefin recovery via chemical absorption

    SciTech Connect

    Barchas, R.

    1998-06-01

    The recovery of fight olefins in petrochemical plants has generally been accomplished through cryogenic distillation, a process which is very capital and energy intensive. In an effort to simplify the recovery process and reduce its cost, BP Chemicals has developed a chemical absorption technology based on an aqueous silver nitrate solution. Stone & Webster is now marketing, licensing, and engineering the technology. The process is commercially ready for recovering olefins from olefin derivative plant vent gases, such as vents from polyethylene, polypropylene, ethylene oxide, and synthetic ethanol units. The process can also be used to debottleneck C{sub 2} or C{sub 3} splinters, or to improve olefin product purity. This paper presents the olefin recovery imp technology, discusses its applications, and presents economics for the recovery of ethylene and propylene.

  16. Graphene-Based Chemical Sensors.

    PubMed

    Yavari, Fazel; Koratkar, Nikhil

    2012-07-01

    Pioneering research in 2004 by Geim and Novoselov (2010 Nobel Prize winners in Physics) of the University of Manchester led to the isolation of a monolayer graphene sheet. Graphene is a single-atom-thick sheet of sp(2) hybridized carbon atoms that are packed in a hexagonal honeycomb crystalline structure. Graphene is the fundamental building block of all sp(2) carbon materials including single-walled carbon nanotubes, mutliwalled carbon nanotubes, and graphite and is therefore interesting from the fundamental standpoint as well as for practical applications. One of the most promising applications of graphene that has emerged so far is its utilization as an ultrasensitive chemical or gas sensor. In this article, we review some of the significant work performed with graphene and its derivatives for gas detection and provide a perspective on the challenges that need to be overcome to enable commercially viable graphene chemical sensor technologies. PMID:26291854

  17. Introduction to Galactic Chemical Evolution

    NASA Astrophysics Data System (ADS)

    Matteucci, Francesca

    2016-04-01

    In this lecture I will introduce the concept of galactic chemical evolution, namely the study of how and where the chemical elements formed and how they were distributed in the stars and gas in galaxies. The main ingredients to build models of galactic chemical evolution will be described. They include: initial conditions, star formation history, stellar nucleosynthesis and gas flows in and out of galaxies. Then some simple analytical models and their solutions will be discussed together with the main criticisms associated to them. The yield per stellar generation will be defined and the hypothesis of instantaneous recycling approximation will be critically discussed. Detailed numerical models of chemical evolution of galaxies of different morphological type, able to follow the time evolution of the abundances of single elements, will be discussed and their predictions will be compared to observational data. The comparisons will include stellar abundances as well as interstellar medium ones, measured in galaxies. I will show how, from these comparisons, one can derive important constraints on stellar nucleosynthesis and galaxy formation mechanisms. Most of the concepts described in this lecture can be found in the monograph by Matteucci (2012).

  18. Proton Chemical-Shift Spectra

    NASA Astrophysics Data System (ADS)

    Simova, Svetlana; Sengstschmid, Helmut; Freeman, Ray

    1997-01-01

    Three related methods are explored for obtaining high-resolution proton spectra without spin-spin splittings, termed "chemical-shift spectra." They are based on two-dimensionalJspectroscopy, where theF1dimension is derived by Fourier transformation of spin-echo modulation. The first technique superimposes theJspectrum on its reflection in theF1= 0 axis, creating multiplet patterns in the form of a St. Andrew's cross. The other two techniques purge certain antiphase product-operator terms, either by dispersal in an inhomogeneous effective radiofrequency field oriented at the magic angle (54.7°) or by means of azfilter. In all three cases, the two-dimensional multiplets are separated by means of a symmetry filter and their centers are taken as a measure of the respective chemical shifts. The 400 MHz proton chemical-shift spectrum of 4-androsten-3,17-dione is presented as an illustrative example. Good separation is achieved, even for interpenetrating spin multiplets with near degeneracies in their chemical shifts. Complications due to strong-coupling effects are discussed.

  19. 40 CFR 721.3560 - Derivative of tetra-chloro-ethy-lene.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Derivative of tetra-chloro-ethy-lene. 721.3560 Section 721.3560 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.3560 Derivative...

  20. 40 CFR 721.4520 - Isopropylidene, bis(1,1-dimethylpropyl) derivative.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Isopropylidene, bis(1,1-dimethylpropyl... Specific Chemical Substances § 721.4520 Isopropylidene, bis(1,1-dimethylpropyl) derivative. (a) Chemical... isopropylidene, bis(1,1-dimethylpropyl) derivative (PMN P-85-648) is subject to reporting under this section...

  1. 40 CFR 721.4520 - Isopropylidene, bis(1,1-dimethylpropyl) derivative.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Isopropylidene, bis(1,1-dimethylpropyl... Specific Chemical Substances § 721.4520 Isopropylidene, bis(1,1-dimethylpropyl) derivative. (a) Chemical... isopropylidene, bis(1,1-dimethylpropyl) derivative (PMN P-85-648) is subject to reporting under this section...

  2. 40 CFR 721.4520 - Isopropylidene, bis(1,1-dimethylpropyl) derivative.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Isopropylidene, bis(1,1-dimethylpropyl... Specific Chemical Substances § 721.4520 Isopropylidene, bis(1,1-dimethylpropyl) derivative. (a) Chemical... isopropylidene, bis(1,1-dimethylpropyl) derivative (PMN P-85-648) is subject to reporting under this section...

  3. 40 CFR 721.4520 - Isopropylidene, bis(1,1-dimethylpropyl) derivative.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Isopropylidene, bis(1,1-dimethylpropyl... Specific Chemical Substances § 721.4520 Isopropylidene, bis(1,1-dimethylpropyl) derivative. (a) Chemical... isopropylidene, bis(1,1-dimethylpropyl) derivative (PMN P-85-648) is subject to reporting under this section...

  4. 40 CFR 721.430 - Oxo-substituted amino-al-kanoic acid derivative.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Oxo-substituted amino-al-kanoic acid... Specific Chemical Substances § 721.430 Oxo-substituted amino-al-kanoic acid derivative. (a) Chemical... as oxo-substituted amino al-kan-oic acid derivative (PMN No. P-92-692) is subject to reporting...

  5. 40 CFR 721.430 - Oxo-substituted amino-al-kanoic acid derivative.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Oxo-substituted amino-al-kanoic acid... Specific Chemical Substances § 721.430 Oxo-substituted amino-al-kanoic acid derivative. (a) Chemical... as oxo-substituted amino al-kan-oic acid derivative (PMN No. P-92-692) is subject to reporting...

  6. 40 CFR 721.430 - Oxo-substituted amino-al-kanoic acid derivative.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Oxo-substituted amino-al-kanoic acid... Specific Chemical Substances § 721.430 Oxo-substituted amino-al-kanoic acid derivative. (a) Chemical... as oxo-substituted amino al-kan-oic acid derivative (PMN No. P-92-692) is subject to reporting...

  7. 40 CFR 721.430 - Oxo-substituted amino-al-kanoic acid derivative.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Oxo-substituted amino-al-kanoic acid... Specific Chemical Substances § 721.430 Oxo-substituted amino-al-kanoic acid derivative. (a) Chemical... as oxo-substituted amino al-kan-oic acid derivative (PMN No. P-92-692) is subject to reporting...

  8. 40 CFR 721.558 - Salt of a fatty alkylamine derivative (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Salt of a fatty alkylamine derivative... Specific Chemical Substances § 721.558 Salt of a fatty alkylamine derivative (generic). Link to an... to reporting. (1) The chemical substance identified generically as a salt of a fatty...

  9. Treatment of biomass to obtain a target chemical

    DOEpatents

    Dunson, Jr., James B.; Tucker, III, Melvin P.; Elander, Richard T.; Hennessey, Susan Marie

    2010-08-24

    Target chemicals were produced using biocatalysts that are able to ferment sugars derived from treated biomass. Sugars were obtained by pretreating biomass under conditions of high solids and low ammonia concentration, followed by saccharification.

  10. Ionospheric chemical releases

    NASA Technical Reports Server (NTRS)

    Bernhardt, Paul A.; Scales, W. A.

    1990-01-01

    Ionospheric plasma density irregularities can be produced by chemical releases into the upper atmosphere. F-region plasma modification occurs by: (1) chemically enhancing the electron number density; (2) chemically reducing the electron population; or (3) physically convecting the plasma from one region to another. The three processes (production, loss, and transport) determine the effectiveness of ionospheric chemical releases in subtle and surprising ways. Initially, a chemical release produces a localized change in plasma density. Subsequent processes, however, can lead to enhanced transport in chemically modified regions. Ionospheric modifications by chemical releases excites artificial enhancements in airglow intensities by exothermic chemical reactions between the newly created plasma species. Numerical models were developed to describe the creation and evolution of large scale density irregularities and airglow clouds generated by artificial means. Experimental data compares favorably with theses models. It was found that chemical releases produce transient, large amplitude perturbations in electron density which can evolve into fine scale irregularities via nonlinear transport properties.

  11. 78 FR 32191 - Derivatives

    Federal Register 2010, 2011, 2012, 2013, 2014

    2013-05-29

    ... alternatives. \\5\\ 71 FR 5155 (February 2, 2012). C. 1998 IRPS This proposed rule is consistent with a 1998... promulgation of this proposed rule. \\7\\ 76 FR 37030 (June 24, 2011). First, the Board asked if it should... derivatives transactions independently. \\9\\ 77 FR 5416 (Feb. 3, 2012). Question One. The Board asked if...

  12. Ferroelectricity in corundum derivatives

    NASA Astrophysics Data System (ADS)

    Ye, Meng; Vanderbilt, David

    2016-04-01

    The search for new ferroelectric (FE) materials holds promise for broadening our understanding of FE mechanisms and extending the range of application of FE materials. Here we investigate a class of A B O3 and A2B B'O6 materials that can be derived from the X2O3 corundum structure by mixing two or three ordered cations on the X site. Most such corundum derivatives have a polar structure, but it is unclear whether the polarization is reversible, which is a requirement for a FE material. In this paper, we propose a method to study the FE reversal path of materials in the corundum derivative family. We first categorize the corundum derivatives into four classes and show that only two of these allow for the possibility of FE reversal. We then calculate the energy profile and energy barrier of the FE reversal path using first-principles density functional methods with a structural constraint. Furthermore, we identify several empirical measures that can provide a rule of thumb for estimating the energy barriers. Finally, the conditions under which the magnetic ordering is compatible with ferroelectricity are determined. These results lead us to predict several potentially new FE materials.

  13. Revisiting the definition of the electronic chemical potential, chemical hardness, and softness at finite temperatures

    NASA Astrophysics Data System (ADS)

    Franco-Pérez, Marco; Gázquez, José L.; Ayers, Paul W.; Vela, Alberto

    2015-10-01

    We extend the definition of the electronic chemical potential (μe) and chemical hardness (ηe) to finite temperatures by considering a reactive chemical species as a true open system to the exchange of electrons, working exclusively within the framework of the grand canonical ensemble. As in the zero temperature derivation of these descriptors, the response of a chemical reagent to electron-transfer is determined by the response of the (average) electronic energy of the system, and not by intrinsic thermodynamic properties like the chemical potential of the electron-reservoir which is, in general, different from the electronic chemical potential, μe. Although the dependence of the electronic energy on electron number qualitatively resembles the piecewise-continuous straight-line profile for low electronic temperatures (up to ca. 5000 K), the introduction of the temperature as a free variable smoothens this profile, so that derivatives (of all orders) of the average electronic energy with respect to the average electron number exist and can be evaluated analytically. Assuming a three-state ensemble, well-known results for the electronic chemical potential at negative (-I), positive (-A), and zero values of the fractional charge (-(I + A)/2) are recovered. Similarly, in the zero temperature limit, the chemical hardness is formally expressed as a Dirac delta function in the particle number and satisfies the well-known reciprocity relation with the global softness.

  14. Platform Chemicals from an Oilseed Biorefinery

    SciTech Connect

    Tupy, Mike; Schrodi Yann

    2006-11-06

    The US chemical industry is $460 billion in size where a $150 billion segment of which is non-oxygenated chemicals that is sourced today via petroleum but is addressable by a renewable feedstock if one considers a more chemically reduced feedstock such as vegetable oils. Vegetable oil, due to its chemical functionality, provides a largely untapped opportunity as a renewable chemical source to replace petroleum-derived chemicals and produce platform chemicals unavailable today. This project examined the fertile intersection between the rich building blocks provided by vegetable oils and the enhanced chemical modification capability provided by metathesis chemistry. The technology advanced in this study is the process of ethylene cross-metathesis (referred to as ethenolysis) with vegetable oil and vegetable oil derivatives to manufacture the platform-chemical 9-decenoic acid (or 9DA) and olefin co-products. The project team meet its goals of demonstrating improved catalyst efficiencies of several multiples, deepening the mechanistic understanding of metathesis, synthesis and screening of dozens of new catalysts, designing and modeling commercial processes, and estimating production costs. One demonstrable result of the study was a step change improvement in catalyst turnover number in the ethenolysis of methyl oleate as reported here. We met our key measurable of producing 100 lbs of 9DA at the pilot-scale, which demonstrated ability to scale-up ethenolysis. DOE Project funding had significant positive impact on development of metathetically modified vegetable oils more broadly as the Cargill/Materia partnership, that was able to initiate primarily due to DOE funding, has succeeded in commercializing products, validating metathesis as a platform technology, and expanding a diverse products portfolio in high value and in large volume markets. Opportunities have expanded and business development has gained considerable momentum and enabled further expansion of the Materia/Cargill relationship. This project exceeded expectations and is having immediate impact on DOE success by replacing petroleum products with renewables in a large volume application today.

  15. 40 CFR 721.3560 - Derivative of tetra-chloro-ethy-lene.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... Health Administration regulations and set forth at 29 CFR 1910.134, and 30 CFR part 11, respectively, and... SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.3560 Derivative of tetra-chloro-ethy-lene. (a) Chemical substance and significant new...

  16. 40 CFR 721.3560 - Derivative of tetra-chloro-ethy-lene.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... Health Administration regulations and set forth at 29 CFR 1910.134, and 30 CFR part 11, respectively, and... SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.3560 Derivative of tetra-chloro-ethy-lene. (a) Chemical substance and significant new...

  17. PREDICTION OF OCTANOL/WATER PARTITION COEFFICIENT (KOW) WITH ALGORITHMICALLY DERIVED VARIABLES

    EPA Science Inventory

    A statistical model was developed with algorithmically derived independent variables based on chemical structure for prediction of octanol/water partition coefficients (Kow) measured for more than 4,000 chemicals. he procedure first classified the chemicals into 14 groups based o...

  18. Chemical Industry Bandwidth Study

    SciTech Connect

    none,

    2006-12-01

    The Chemical Bandwidth Study provides a snapshot of potentially recoverable energy losses during chemical manufacturing. The advantage of this study is the use of "exergy" analysis as a tool for pinpointing inefficiencies.

  19. Capacitive chemical sensor

    DOEpatents

    Manginell, Ronald P; Moorman, Matthew W; Wheeler, David R

    2014-05-27

    A microfabricated capacitive chemical sensor can be used as an autonomous chemical sensor or as an analyte-sensitive chemical preconcentrator in a larger microanalytical system. The capacitive chemical sensor detects changes in sensing film dielectric properties, such as the dielectric constant, conductivity, or dimensionality. These changes result from the interaction of a target analyte with the sensing film. This capability provides a low-power, self-heating chemical sensor suitable for remote and unattended sensing applications. The capacitive chemical sensor also enables a smart, analyte-sensitive chemical preconcentrator. After sorption of the sample by the sensing film, the film can be rapidly heated to release the sample for further analysis. Therefore, the capacitive chemical sensor can optimize the sample collection time prior to release to enable the rapid and accurate analysis of analytes by a microanalytical system.

  20. Chemical Engineering Division Activities

    ERIC Educational Resources Information Center

    Chemical Engineering Education, 1978

    1978-01-01

    The 1978 ASEE Chemical Engineering Division Lecturer was Theodore Vermeulen of the University of California at Berkeley. Other chemical engineers who received awards or special recognition at a recent ASEE annual conference are mentioned. (BB)