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Sample records for elimination par catalyse

  1. [Investigation of a measles outbreak in Pará State, Brazil, in the age of elimination of the disease].

    PubMed

    Jesus, Hiane Santos de; Nascimento, Gilmara Lima; Rosa, Fabiano Marques; Santos, Deise Aparecida dos

    2015-10-01

    In July 27th, 2010, witnessed the late notification of a positive test result for measles IgM antibodies in Belém, Pará State, Brazil, sparking an epidemiological investigation and control and preventive measures. Two more confirmed cases were identified, both of whom were siblings of the index case, with clinical signs and symptoms and incubation period consistent with measles. We conducted a retrospective search in hospitals and laboratories for suspected cases that lived in or had visited Pará State from May 1st to August 4th, 2010, and had presented fever and exanthema accompanied by cough and/or sneezing and/or conjunctivitis. All identified cases were investigated by telephone contact and/or home visits. We reviewed 183,854 consultation forms and identified 56 (0.03%) suspected cases. We applied 2,535 doses of triple viral vaccine distributed between blockades vaccination intensifications. A household measles outbreak occurred in Belém with the detection and isolation of a viral genotype imported from Europe. Timely and sensitive epidemiological surveillance is recommended for the detection of suspected cases of measles and maintenance of high immunization coverage.

  2. [Investigation of a measles outbreak in Pará State, Brazil, in the age of elimination of the disease].

    PubMed

    Jesus, Hiane Santos de; Nascimento, Gilmara Lima; Rosa, Fabiano Marques; Santos, Deise Aparecida dos

    2015-10-01

    In July 27th, 2010, witnessed the late notification of a positive test result for measles IgM antibodies in Belém, Pará State, Brazil, sparking an epidemiological investigation and control and preventive measures. Two more confirmed cases were identified, both of whom were siblings of the index case, with clinical signs and symptoms and incubation period consistent with measles. We conducted a retrospective search in hospitals and laboratories for suspected cases that lived in or had visited Pará State from May 1st to August 4th, 2010, and had presented fever and exanthema accompanied by cough and/or sneezing and/or conjunctivitis. All identified cases were investigated by telephone contact and/or home visits. We reviewed 183,854 consultation forms and identified 56 (0.03%) suspected cases. We applied 2,535 doses of triple viral vaccine distributed between blockades vaccination intensifications. A household measles outbreak occurred in Belém with the detection and isolation of a viral genotype imported from Europe. Timely and sensitive epidemiological surveillance is recommended for the detection of suspected cases of measles and maintenance of high immunization coverage. PMID:26735390

  3. A study on the AMACR catalysed elimination reaction and its application to inhibitor testing† †Electronic supplementary information (ESI) available: 1H NMR spectra of synthesised compounds; details of X-ray crystal structure determination of compound 35; original data for Table 1; plots of fluorescence resulting from reaction of sensors 33 and 34 with fluoride solutions. CCDC 1408401. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c5ob01541c Click here for additional data file. Click here for additional data file.

    PubMed Central

    Yevglevskis, Maksims; Lee, Guat L.; Sun, Jenny; Zhou, Shiyi; Sun, Xiaolong; Kociok-Köhn, Gabriele; James, Tony D.; Woodman, Timothy J.

    2016-01-01

    α-Methylacyl-CoA racemase (AMACR; P504S) catalyses a key step in the degradation of branched-chain fatty acids and is important for the pharmacological activation of Ibuprofen and related drugs. Levels of AMACR are increased in prostate and other cancers, and it is a drug target. Development of AMACR as a drug target is hampered by lack of a convenient assay. AMACR irreversibly catalyses the elimination of HF from 3-fluoro-2-methylacyl-CoA substrates, and this reaction was investigated for use as an assay. Several known inhibitors and alternative substrates reduced conversion of 3-fluoro-2-methyldecanoyl-CoA by AMACR, as determined by 1H NMR. The greatest reduction of activity was observed with known potent inhibitors. A series of novel acyl-CoA esters with aromatic side chains were synthesised for testing as chromophoric substrates. These acyl-CoA esters were converted to unsaturated products by AMACR, but their use was limited by non-enzymatic elimination. Fluoride sensors were also investigated as a method of quantifying released fluoride and thus AMACR activity. These sensors generally suffered from high background signal and lacked reproducibility under the assay conditions. In summary, the elimination reaction can be used to characterise inhibitors, but it was not possible to develop a convenient colorimetric or fluorescent assay using 3-fluoro-2-methylacyl-CoA substrates. PMID:26537174

  4. THE MEASURES PAR PROJECT

    NASA Astrophysics Data System (ADS)

    Frouin, R. J.; Franz, B.

    2009-12-01

    The solar energy available for photosynthesis, known as PAR, controls the growth of phytoplankton and, therefore, regulates the composition and evolution of marine ecosystems. Knowing the spatial and temporal distribution of PAR over the oceans is critical to understanding biogeochemical cycles of carbon, nutrients, and oxygen, and to address important climate and global change issues such as the fate of anthropogenic atmospheric carbon dioxide. In view of this, a 12-year time series of PAR at the ocean surface, starting in September 1997, is being produced by the NASA Ocean Biology Processing Group from SeaWiFS, MODIS-Terra, and MODIS-Aqua data. The product covers the global oceans, with a spatial resolution of about 9.3x9.3 km (equal area grid) and a temporal resolution of one day. PAR is computed as the difference between the 400-700 nm solar flux incident on the top of the atmosphere (known) and reflected back to space by the atmosphere and surface (derived from satellite radiance), taking into account atmospheric absorption (modeled). Knowledge of pixel composition is not required, eliminating the need for cloud screening and arbitrary assumptions about sub-pixel cloudiness. Combining data from satellite sensors with different equatorial crossing times accounts for the diurnal variability of clouds and, therefore, increases accuracy on a daily time scale. The processing system, including routine check of accuracy and control of quality, is designed to operate during the entire lifetime of SeaWiFS and MODIS, and to accommodate future sensors with ocean-color capabilities. Maps of daily, weekly, and monthly PAR obtained from individual sensors are presented, as well as merged products. Accuracy is quantified in comparisons with other satellite estimates, the National Centers for Environmental Prediction reanalysis product, and in-situ measurements from fixed buoys and platforms. The good statistical performance makes the satellite PAR product suitable for large

  5. Symbiosis catalyses niche expansion and diversification

    PubMed Central

    Joy, Jeffrey B.

    2013-01-01

    Interactions between species are important catalysts of the evolutionary processes that generate the remarkable diversity of life. Symbioses, conspicuous and inherently interesting forms of species interaction, are pervasive throughout the tree of life. However, nearly all studies of the impact of species interactions on diversification have concentrated on competition and predation leaving unclear the importance of symbiotic interaction. Here, I show that, as predicted by evolutionary theories of symbiosis and diversification, multiple origins of a key innovation, symbiosis between gall-inducing insects and fungi, catalysed both expansion in resource use (niche expansion) and diversification. Symbiotic lineages have undergone a more than sevenfold expansion in the range of host-plant taxa they use relative to lineages without such fungal symbionts, as defined by the genetic distance between host plants. Furthermore, symbiotic gall-inducing insects are more than 17 times as diverse as their non-symbiotic relatives. These results demonstrate that the evolution of symbiotic interaction leads to niche expansion, which in turn catalyses diversification. PMID:23390106

  6. The mechanism of Rubisco-catalysed oxygenation.

    PubMed

    Tcherkez, Guillaume

    2016-05-01

    Ribulose-1,5-bisphosphate carboxylase/oxygenase (Rubisco) is the cornerstone of photosynthetic carbon assimilation because it catalyses the fixation of CO2 onto ribulose-1,5-bisphosphate (RuBP). The enzyme also catalyses RuBP oxygenation, thereby evolving phosphoglycolate which is recycled along the photorespiratory pathway. Oxygenation is quantitatively important, because under ordinary gaseous conditions, more than one third of RuBP molecules are oxygenated rather than carboxylated. However, contrary to carboxylation, the chemical mechanism of oxygenation is not well known, and little progress has been made since the early 80s. Here, I review recent experimental data that provide some new insights into the reaction mechanism, and carry out simple calculations of kinetic parameters. Isotope effects suggest that oxygenation is less likely initiated by a redox phenomenon (such as superoxide production) and more likely involves concerted chemical events that imply interactions with protons. A possible energy profile of the reaction is drawn which suggests that the generation of the oxygenated reaction intermediate (peroxide) is irreversible. Possible changes in oxygenation-associated rate constants between Rubisco forms are discussed. PMID:26286702

  7. RNA-catalysed synthesis of complementary-strand RNA

    NASA Astrophysics Data System (ADS)

    Doudna, Jennifer A.; Szostak, Jack W.

    1989-06-01

    The Tetrahymena ribozyme can splice together multiple oligonucleotides aligned on a template strand to yield a fully complementary product strand. This reaction demonstrates the feasibility of RNA-catalysed RNA replications.

  8. Investigation of copper(II) tetrafluoroborate catalysed epoxide opening

    PubMed Central

    Capes, Amy S.; Crossman, Arthur T.; Webster, Lauren A.; Ferguson, Michael A.J.; Gilbert, Ian H.

    2011-01-01

    We report the extension of the copper(II) tetrafluoroborate catalysed opening of epoxides with alcohols to include a wider variety of alcohols, a range of solvents and a method to purify the products from the reaction. PMID:22505782

  9. Enzyme-catalysed conjugations of glutathione with unsaturated compounds

    PubMed Central

    Boyland, E.; Chasseaud, L. F.

    1967-01-01

    1. Rat-liver supernatant catalyses the reaction of diethyl maleate with glutathione. 2. Evidence is presented that the enzyme involved is different from the known glutathione-conjugating enzymes, glutathione S-alkyltransferase, S-aryltransferase and S-epoxidetransferase. 3. Rat-liver supernatant catalyses the reaction of a number of other αβ-unsaturated compounds, including aldehydes, ketones, lactones, nitriles and nitro compounds, with glutathione: separate enzymes may be responsible for these reactions. PMID:6035529

  10. Dynamics of Radical-Mediated Enzyme Catalyses

    NASA Astrophysics Data System (ADS)

    Warncke, Kurt

    1997-11-01

    An emergent class of enzymes harnesses the extreme reactivity of electron-deficient free radical species to perform some of the most difficult reactions in biology. The regio- and stereo-selectivity achieved by these enzymes defies long-held ideas that radical reactions are non-specific. The common primary step in these catalyses is metal- or metallocenter-assisted generation of an electron-deficient organic "initiator radical". The initiator radical abstracts a hydrogen atom from the substrate, opening a new reaction channel for rearrangement to the product. Our aim is to elucidate the detailed molecular mechanisms of the radical pair separation and radical rearrangement steps. Radical pair separation and substrate radical rearrangement are tracked by using time-resolved (10-7 to 10-3 s) techniques of pulsed-electron paramagnetic resonance spectroscopy (FT-EPR, ESEEM). Synchronous time-evolution of the reactions is attained by triggering with a visible laser pulse. Transient non-Boltzmann population of the states of the spin-coupled systems, and resultant electron spin polarization, facilitates study at or near room temperature under conditions where the enzymes are operative. The systems examined include ethanolamine deaminase, a vitamin B12 coenzyme-dependent enzyme, ribonucleotide reductase and photosynthetic reaction centers. The electronic and nuclear structural and kinetic information obtained from the pulsed-EPR studies is used to address how the initiator radicals are stabilized against deleterious recombination with the metal, and to distinguish the participation of concerted versus sequential rearrangement pathways.

  11. Iron-catalysed tritiation of pharmaceuticals.

    PubMed

    Yu, Renyuan Pony; Hesk, David; Rivera, Nelo; Pelczer, István; Chirik, Paul J

    2016-01-14

    A thorough understanding of the pharmacokinetic and pharmacodynamic properties of a drug in animal models is a critical component of drug discovery and development. Such studies are performed in vivo and in vitro at various stages of the development process--ranging from preclinical absorption, distribution, metabolism and excretion (ADME) studies to late-stage human clinical trials--to elucidate a drug molecule's metabolic profile and to assess its toxicity. Radiolabelled compounds, typically those that contain (14)C or (3)H isotopes, are one of the most powerful and widely deployed diagnostics for these studies. The introduction of radiolabels using synthetic chemistry enables the direct tracing of the drug molecule without substantially altering its structure or function. The ubiquity of C-H bonds in drugs and the relative ease and low cost associated with tritium ((3)H) make it an ideal radioisotope with which to conduct ADME studies early in the drug development process. Here we describe an iron-catalysed method for the direct (3)H labelling of pharmaceuticals by hydrogen isotope exchange, using tritium gas as the source of the radioisotope. The site selectivity of the iron catalyst is orthogonal to currently used iridium catalysts and allows isotopic labelling of complementary positions in drug molecules, providing a new diagnostic tool in drug development.

  12. Iron-catalysed tritiation of pharmaceuticals

    NASA Astrophysics Data System (ADS)

    Pony Yu, Renyuan; Hesk, David; Rivera, Nelo; Pelczer, István; Chirik, Paul J.

    2016-01-01

    A thorough understanding of the pharmacokinetic and pharmacodynamic properties of a drug in animal models is a critical component of drug discovery and development. Such studies are performed in vivo and in vitro at various stages of the development process—ranging from preclinical absorption, distribution, metabolism and excretion (ADME) studies to late-stage human clinical trials—to elucidate a drug molecule’s metabolic profile and to assess its toxicity. Radiolabelled compounds, typically those that contain 14C or 3H isotopes, are one of the most powerful and widely deployed diagnostics for these studies. The introduction of radiolabels using synthetic chemistry enables the direct tracing of the drug molecule without substantially altering its structure or function. The ubiquity of C-H bonds in drugs and the relative ease and low cost associated with tritium (3H) make it an ideal radioisotope with which to conduct ADME studies early in the drug development process. Here we describe an iron-catalysed method for the direct 3H labelling of pharmaceuticals by hydrogen isotope exchange, using tritium gas as the source of the radioisotope. The site selectivity of the iron catalyst is orthogonal to currently used iridium catalysts and allows isotopic labelling of complementary positions in drug molecules, providing a new diagnostic tool in drug development.

  13. Iron-catalysed tritiation of pharmaceuticals.

    PubMed

    Yu, Renyuan Pony; Hesk, David; Rivera, Nelo; Pelczer, István; Chirik, Paul J

    2016-01-14

    A thorough understanding of the pharmacokinetic and pharmacodynamic properties of a drug in animal models is a critical component of drug discovery and development. Such studies are performed in vivo and in vitro at various stages of the development process--ranging from preclinical absorption, distribution, metabolism and excretion (ADME) studies to late-stage human clinical trials--to elucidate a drug molecule's metabolic profile and to assess its toxicity. Radiolabelled compounds, typically those that contain (14)C or (3)H isotopes, are one of the most powerful and widely deployed diagnostics for these studies. The introduction of radiolabels using synthetic chemistry enables the direct tracing of the drug molecule without substantially altering its structure or function. The ubiquity of C-H bonds in drugs and the relative ease and low cost associated with tritium ((3)H) make it an ideal radioisotope with which to conduct ADME studies early in the drug development process. Here we describe an iron-catalysed method for the direct (3)H labelling of pharmaceuticals by hydrogen isotope exchange, using tritium gas as the source of the radioisotope. The site selectivity of the iron catalyst is orthogonal to currently used iridium catalysts and allows isotopic labelling of complementary positions in drug molecules, providing a new diagnostic tool in drug development. PMID:26762456

  14. De Par en Par (Wide Open), 1993.

    ERIC Educational Resources Information Center

    De Par en Par, 1993

    1993-01-01

    This document consists of the four issues of the serial "De Par en Par" published during 1993. This serial provides lessons in Spanish for elementary school children. It is written by bilingual education teachers for use in the bilingual classroom. The magazine bases itself on the K-6 curriculum and offers a variety of activities for classroom…

  15. Palladium/N-heterocyclic carbene catalysed regio and diastereoselective reaction of ketones with allyl reagents via inner-sphere mechanism

    PubMed Central

    Bai, Da-Chang; Yu, Fei-Le; Wang, Wan-Ying; Chen, Di; Li, Hao; Liu, Qing-Rong; Ding, Chang-Hua; Chen, Bo; Hou, Xue-Long

    2016-01-01

    The palladium-catalysed allylic substitution reaction is one of the most important reactions in transition-metal catalysis and has been well-studied in the past decades. Most of the reactions proceed through an outer-sphere mechanism, affording linear products when monosubstituted allyl reagents are used. Here, we report an efficient Palladium-catalysed protocol for reactions of β-substituted ketones with monosubstituted allyl substrates, simply by using N-heterocyclic carbene as ligand, leading to branched products with up to three contiguous stereocentres in a (syn, anti)-mode with excellent regio and diastereoselectivities. The scope of the protocol in organic synthesis has been examined preliminarily. Mechanistic studies by both experiments and density functional theory (DFT) calculations reveal that the reaction proceeds via an inner-sphere mechanism—nucleophilic attack of enolate oxygen on Palladium followed by C–C bond-forming [3,3']-reductive elimination. PMID:27283477

  16. Biohydrogen production from kitchen based vegetable waste: effect of pyrolysis temperature and time on catalysed and non-catalysed operation.

    PubMed

    Agarwal, Manu; Tardio, James; Mohan, S Venkata

    2013-02-01

    Pyrolysis of kitchen based vegetable waste (KVW) was studied in a designed packed bed reactor. The effect of process parameters like temperature, time and catalyst on bio-gas yield and its composition was studied. The total bio-gas yield was found to be maximum with non-catalysed operation (260ml/g) at 1073K (180min). Higher hydrogen (H(2)) yield with non-catalysed operation (32.68%) was observed at 1073K (180min) while with catalysed operation the requisite temperature (873K) and time (120min) reduced with both silica gel (33.34%) and sand (41.82%) thus, saving energy input. Methane (CH(4)) yield was found to be highest (4.44times than non-catalysed and 1.42 with silica gel) in presence of sand (71.485ml/g) at medium temperature (873K) and time (60min). The catalyst operation reduced the carbondioxide (CO(2)) share from 47.29% to 41.30% (silica gel catalysed) and 21.91% (sand catalysed) at 873K.

  17. Biohydrogen production from kitchen based vegetable waste: effect of pyrolysis temperature and time on catalysed and non-catalysed operation.

    PubMed

    Agarwal, Manu; Tardio, James; Mohan, S Venkata

    2013-02-01

    Pyrolysis of kitchen based vegetable waste (KVW) was studied in a designed packed bed reactor. The effect of process parameters like temperature, time and catalyst on bio-gas yield and its composition was studied. The total bio-gas yield was found to be maximum with non-catalysed operation (260ml/g) at 1073K (180min). Higher hydrogen (H(2)) yield with non-catalysed operation (32.68%) was observed at 1073K (180min) while with catalysed operation the requisite temperature (873K) and time (120min) reduced with both silica gel (33.34%) and sand (41.82%) thus, saving energy input. Methane (CH(4)) yield was found to be highest (4.44times than non-catalysed and 1.42 with silica gel) in presence of sand (71.485ml/g) at medium temperature (873K) and time (60min). The catalyst operation reduced the carbondioxide (CO(2)) share from 47.29% to 41.30% (silica gel catalysed) and 21.91% (sand catalysed) at 873K. PMID:23313698

  18. Key processes in ruthenium-catalysed olefin metathesis.

    PubMed

    Nelson, David J; Manzini, Simone; Urbina-Blanco, César A; Nolan, Steven P

    2014-09-18

    While the fundamental series of [2+2]cycloadditions and retro[2+2]cycloadditions that make up the pathways of ruthenium-catalysed metathesis reactions is well-established, the exploration of mechanistic aspects of alkene metathesis continues. In this Feature Article, modern mechanistic studies of the alkene metathesis reaction, catalysed by well-defined ruthenium complexes, are discussed. Broadly, these concern the processes of pre-catalyst initiation, propagation and decomposition, which all have a considerable impact on the overall efficiency of metathesis reactions. PMID:24931143

  19. A practical guide to modelling enzyme-catalysed reactions

    PubMed Central

    Lonsdale, Richard; Harvey, Jeremy N.; Mulholland, Adrian J.

    2012-01-01

    Molecular modelling and simulation methods are increasingly at the forefront of elucidating mechanisms of enzyme-catalysed reactions, and shedding light on the determinants of specificity and efficiency of catalysis. These methods have the potential to assist in drug discovery and the design of novel protein catalysts. This Tutorial Review highlights some of the most widely used modelling methods and some successful applications. Modelling protocols commonly applied in studying enzyme-catalysed reactions are outlined here, and some practical implications are considered, with cytochrome P450 enzymes used as a specific example. PMID:22278388

  20. Key processes in ruthenium-catalysed olefin metathesis.

    PubMed

    Nelson, David J; Manzini, Simone; Urbina-Blanco, César A; Nolan, Steven P

    2014-09-18

    While the fundamental series of [2+2]cycloadditions and retro[2+2]cycloadditions that make up the pathways of ruthenium-catalysed metathesis reactions is well-established, the exploration of mechanistic aspects of alkene metathesis continues. In this Feature Article, modern mechanistic studies of the alkene metathesis reaction, catalysed by well-defined ruthenium complexes, are discussed. Broadly, these concern the processes of pre-catalyst initiation, propagation and decomposition, which all have a considerable impact on the overall efficiency of metathesis reactions.

  1. Pars Injuries in Athletes.

    PubMed

    Oren, Jonathan H; Gallina, Jason M

    2016-03-01

    Pars injuries are common causes of low back pain in adolescent athletes. Workup traditionally has included lumbar radiographs with oblique views and single-photon emission computed tomography (SPECT). However, recent literature has demonstrated the accuracy of MRI as a diagnostic modality. Acute injuries may be amenable to bracing with the goal of a healed lesion. Most cases of spondylolysis will result in asymptomatic non-union, though pars repair is an option for symptomatic pars defects without spondylolisthesis. PMID:26977552

  2. Four acid-catalysed dehydration reactions proceed without interference.

    PubMed

    Lirag, Rio Carlo; Miljanić, Ognjen Š

    2014-08-25

    Four acid-catalysed dehydration reactions can proceed in one pot, simultaneously and without interference, to yield one imine, one acetal (or boronic ester), one ester and one alkene, even though many other cross-products could be conceived. This advanced self-sorting behaviour is attributed to different dehydration rates, brought about by dissimilar electronic properties of starting materials.

  3. Nonconsecutive Pars Interarticularis Defects.

    PubMed

    Elgafy, Hossein; Hart, Ryan C; Tanios, Mina

    2015-12-01

    Lumbar spondylolysis is a well-recognized condition occurring in adolescents because of repetitive overuse in sports. Nonconsecutive spondylolysis involving the lumbar spine is rare. In contrast to single-level pars defects that respond well to conservative treatment, there is no consensus about the management of multiple-level pars fractures; a few reports indicated that conservative management is successful, and the majority acknowledged that surgery is often required. The current study presents a rare case of pars fracture involving nonconsecutive segments and discusses the management options. In this case report, we review the patient's history, clinical examination, radiologic findings, and management, as well as the relevant literature. An 18-year-old man presented to the clinic with worsening lower back pain related to nonconsecutive pars fractures at L2 and L5. After 6 months of conservative management, diagnostic computed tomography-guided pars block was used to localize the symptomatic level at L2, which was treated surgically; the L5 asymptomatic pars fracture did not require surgery. At the last follow-up 2 years after surgery, the patient was playing baseball and basketball, and denied any back pain. This article reports a case of rare nonconsecutive pars fractures. Conservative management for at least 6 months is recommended. Successful management depends on the choice of appropriate treatment for each level. Single-photon emission computed tomography scan, and computed tomography-guided pars block are valuable preoperative tools to identify the symptomatic level in such a case. PMID:26665257

  4. Nonconsecutive Pars Interarticularis Defects.

    PubMed

    Elgafy, Hossein; Hart, Ryan C; Tanios, Mina

    2015-12-01

    Lumbar spondylolysis is a well-recognized condition occurring in adolescents because of repetitive overuse in sports. Nonconsecutive spondylolysis involving the lumbar spine is rare. In contrast to single-level pars defects that respond well to conservative treatment, there is no consensus about the management of multiple-level pars fractures; a few reports indicated that conservative management is successful, and the majority acknowledged that surgery is often required. The current study presents a rare case of pars fracture involving nonconsecutive segments and discusses the management options. In this case report, we review the patient's history, clinical examination, radiologic findings, and management, as well as the relevant literature. An 18-year-old man presented to the clinic with worsening lower back pain related to nonconsecutive pars fractures at L2 and L5. After 6 months of conservative management, diagnostic computed tomography-guided pars block was used to localize the symptomatic level at L2, which was treated surgically; the L5 asymptomatic pars fracture did not require surgery. At the last follow-up 2 years after surgery, the patient was playing baseball and basketball, and denied any back pain. This article reports a case of rare nonconsecutive pars fractures. Conservative management for at least 6 months is recommended. Successful management depends on the choice of appropriate treatment for each level. Single-photon emission computed tomography scan, and computed tomography-guided pars block are valuable preoperative tools to identify the symptomatic level in such a case.

  5. Enzyme-catalysed assembly of DNA hydrogel

    NASA Astrophysics Data System (ADS)

    Um, Soong Ho; Lee, Jong Bum; Park, Nokyoung; Kwon, Sang Yeon; Umbach, Christopher C.; Luo, Dan

    2006-10-01

    DNA is a remarkable polymer that can be manipulated by a large number of molecular tools including enzymes. A variety of geometric objects, periodic arrays and nanoscale devices have been constructed. Previously we synthesized dendrimer-like DNA and DNA nanobarcodes from branched DNA via ligases. Here we report the construction of a hydrogel entirely from branched DNA that are three-dimensional and can be crosslinked in nature. These DNA hydrogels were biocompatible, biodegradable, inexpensive to fabricate and easily moulded into desired shapes and sizes. The distinct difference of the DNA hydrogel to other bio-inspired hydrogels (including peptide-based, alginate-based and DNA (linear)-polyacrylamide hydrogels) is that the crosslinking is realized via efficient, ligase-mediated reactions. The advantage is that the gelling processes are achieved under physiological conditions and the encapsulations are accomplished in situ-drugs including proteins and even live mammalian cells can be encapsulated in the liquid phase eliminating the drug-loading step and also avoiding denaturing conditions. Fine tuning of these hydrogels is easily accomplished by adjusting the initial concentrations and types of branched DNA monomers, thus allowing the hydrogels to be tailored for specific applications such as controlled drug delivery, tissue engineering, 3D cell culture, cell transplant therapy and other biomedical applications.

  6. Par Pond water balance

    SciTech Connect

    Hiergesell, R.A.; Dixon, K.L.

    1996-06-01

    A water budget for the Par Pond hydrologic system was established in order to estimate the rate of groundwater influx to Par Pond. This estimate will be used in modeling exercises to predict Par Pond reservoir elevation and spillway discharge in the scenario where Savannah River water is no longer pumped and discharged into Par Pond. The principal of conservation of mass was used to develop the water budget, where water inflow was set equal to water outflow. Components of the water budget were identified, and the flux associated with each was determined. The water budget was considered balanced when inflow and outflow summed to zero. The results of this study suggest that Par Pond gains water from the groundwater system in the upper reaches of the reservoir, but looses water to the groundwater system near the dam. The rate of flux of groundwater from the water table aquifer into Par Pond was determined to be 13 cfs. The rate of flux from Par Pond to the water table aquifer near the dam was determined to be 7 cfs.

  7. Nickel-catalysed Suzuki-Miyaura coupling of amides

    NASA Astrophysics Data System (ADS)

    Weires, Nicholas A.; Baker, Emma L.; Garg, Neil K.

    2016-01-01

    The Suzuki-Miyaura coupling has become one of the most important and prevalent methods for the construction of C-C bonds. Although palladium catalysis has historically dominated the field, the use of nickel catalysis has become increasingly widespread because of its unique ability to cleave carbon-heteroatom bonds that are unreactive towards other transition metals. We report the first nickel-catalysed Suzuki-Miyaura coupling of amides, which proceeds by an uncommon cleavage of the amide C-N bond after N-tert-butoxycarbonyl activation. The methodology is mild, functional-group tolerant and can be strategically employed in sequential transition-metal-catalysed cross-coupling sequences to unite heterocyclic fragments. These studies demonstrate that amides, despite classically considered inert substrates, can be harnessed as synthons for use in reactions that form C-C bonds through cleavage of the C-N bond using non-precious metal catalysis.

  8. Degradation of C-hordein by metal-catalysed oxidation.

    PubMed

    Huang, Xin; Kanerva, Päivi; Salovaara, Hannu; Sontag-Strohm, Tuula

    2016-04-01

    C-hordein is a monomeric prolamin protein in barley. The unusual primary structure of C-hordein has highly repetitive sequences and forms a secondary structure of beta-turns. C-hordein structure is similar to that of collagen protein, whose degradation by metal-catalysed oxidation has been intensively studied. No information exists on the metal catalysed oxidation of C-hordein, however. In this study, copper-catalysed hydrogen peroxide induced oxidation of C-hordein caused substantial degradation and formed some insoluble compounds. The use of a gliadin standard in R5 ELISA determinations causes an overestimation of hordeins in a sample. A C-hordein standard was therefore directly used as a standard, thus allowing the C-hordein to be analysed as its oxidised prolamin product. After 48 h of oxidation, the prolamin concentration of oxidised C-hordein decreased to 20% of its original amount for competitive ELISA, and to 3% for sandwich ELISA methods. Carbonyl groups were formed during the oxidation. Backbone fragmentation and side-chain modification suggested structural changes of R5 epitopes in C-hordein. Oxidation is an alternative to enzymatic hydrolysis when degrading and modifying C-hordein.

  9. Microbially induced and microbially catalysed precipitation: two different carbonate factories

    NASA Astrophysics Data System (ADS)

    Meister, Patrick

    2016-04-01

    The landmark paper by Schlager (2003) has revealed three types of benthic carbonate production referred to as "carbonate factories", operative at different locations at different times in Earth history. The tropical or T-factory comprises the classical platforms and fringing reefs and is dominated by carbonate precipitation by autotrophic calcifying metazoans ("biotically controlled" precipitation). The cool or C-factory is also biotically controlled but via heterotrophic, calcifying metazoans in cold and deep waters at the continental margins. A further type is the mud-mound or M-factory, where carbonate precipitation is supported by microorganisms but not controlled by a specific enzymatic pathway ("biotically induced" precipitation). How exactly the microbes influence precipitation is still poorly understood. Based on recent experimental and field studies, the microbial influence on modern mud mound and microbialite growth includes two fundamentally different processes: (1) Metabolic activity of microbes may increase the saturation state with respect to a particular mineral phase, thereby indirectly driving the precipitation of the mineral phase: microbially induced precipitation. (2) In a situation, where a solution is already supersaturated but precipitation of the mineral is inhibited by a kinetic barrier, microbes may act as a catalyser, i.e. they lower the kinetic barrier: microbially catalysed precipitation. Such a catalytic effect can occur e.g. via secreted polymeric substances or specific chemical groups on the cell surface, at which the minerals nucleate or which facilitate mechanistically the bonding of new ions to the mineral surface. Based on these latest developments in microbialite formation, I propose to extend the scheme of benthic carbonate factories of Schlager et al. (2003) by introducing an additional branch distinguishing microbially induced from microbially catalysed precipitation. Although both mechanisms could be operative in a M

  10. Slanted baffle mist eliminator

    DOEpatents

    Vance, Richard F.

    1995-11-07

    An apparatus for the elimination of mist from off-gas during vitrification f nuclear waste, where baffles are installed on a slant toward the flow of the off-gasses eliminating the need to expand the cross-sectional area of the duct size.

  11. Slanted baffle mist eliminator

    DOEpatents

    Vance, Richard F.

    1995-01-01

    An apparatus for the elimination of mist from off-gas during vitrification f nuclear waste, where baffles are installed on a slant toward the flow of the off-gasses eliminating the need to expand the cross-sectional area of the duct size.

  12. Palladium/N-heterocyclic carbene catalysed regio and diastereoselective reaction of ketones with allyl reagents via inner-sphere mechanism

    DOE PAGES

    Bai, Da -Chang; Yu, Fei -Le; Wang, Wan -Ying; Chen, Di; Li, Hao; Liu, Qing -Rong; Ding, Chang -Hua; Chen, Bo; Hou, Xue -Long

    2016-06-10

    The palladium-catalysed allylic substitution reaction is one of the most important reactions in transition-metal catalysis and has been well-studied in the past decades. Most of the reactions proceed through an outer-sphere mechanism, affording linear products when monosubstituted allyl reagents are used. Here, we report an efficient Palladium-catalysed protocol for reactions of beta-substituted ketones with monosubstituted allyl substrates, simply by using N-heterocyclic carbene as ligand, leading to branched products with up to three contiguous stereocentres in a (syn, anti)-mode with excellent regio and diastereoselectivities. The scope of the protocol in organic synthesis has been examined preliminarily. As a result, mechanistic studiesmore » by both experiments and density functional theory ( DFT) calculations reveal that the reaction proceeds via an inner-sphere mechanism-nucleophilic attack of enolate oxygen on Palladium followed by C-C bond-forming [3,3']-reductive elimination.« less

  13. Peroxidase-catalysed interfacial adhesion of aquatic caddisworm silk.

    PubMed

    Wang, Ching-Shuen; Pan, Huaizhong; Weerasekare, G Mahika; Stewart, Russell J

    2015-11-01

    Casemaker caddisfly (Hesperophylax occidentalis) larvae use adhesive silk fibres to construct protective shelters under water. The silk comprises a distinct peripheral coating on a viscoelastic fibre core. Caddisworm silk peroxinectin (csPxt), a haem-peroxidase, was shown to be glycosylated by lectin affinity chromatography and tandem mass spectrometry. Using high-resolution H2O2 and peroxidase-dependent silver ion reduction and nanoparticle deposition, imaged by electron microscopy, csPxt activity was shown to be localized in the peripheral layer of drawn silk fibres. CsPxt catalyses dityrosine cross-linking within the adhesive peripheral layer post-draw, initiated perhaps by H2O2 generated by a silk gland-specific superoxide dismutase 3 (csSOD3) from environmental reactive oxygen species present in natural water. CsSOD3 was also shown to be a glycoprotein and is likely localized in the peripheral layer. Using a synthetic fluorescent phenolic copolymer and confocal microscopy, it was shown that csPxt catalyses oxidative cross-linking to external polyphenolic compounds capable of diffusive interpenetration into the fuzzy peripheral coating, including humic acid, a natural surface-active polyphenol. The results provide evidence of enzyme-mediated covalent cross-linking of a natural bioadhesive to polyphenol conditioned interfaces as a mechanism of permanent adhesion underwater. PMID:26490632

  14. Universal leakage elimination

    SciTech Connect

    Byrd, Mark S.; Lidar, Daniel A.; Wu, L.-A.; Zanardi, Paolo

    2005-05-15

    'Leakage' errors are particularly serious errors which couple states within a code subspace to states outside of that subspace, thus destroying the error protection benefit afforded by an encoded state. We generalize an earlier method for producing leakage elimination decoupling operations and examine the effects of the leakage eliminating operations on decoherence-free or noiseless subsystems which encode one logical, or protected qubit into three or four qubits. We find that by eliminating a large class of leakage errors, under some circumstances, we can create the conditions for a decoherence-free evolution. In other cases we identify a combined decoherence-free and quantum error correcting code which could eliminate errors in solid-state qubits with anisotropic exchange interaction Hamiltonians and enable universal quantum computing with only these interactions.

  15. La pelade par plaques

    PubMed Central

    Spano, Frank; Donovan, Jeff C.

    2015-01-01

    Résumé Objectif Présenter aux médecins de famille des renseignements de base pour faire comprendre l’épidémiologie, la pathogenèse, l’histologie et l’approche clinique au diagnostic de la pelade par plaques. Sources des données Une recension a été effectuée dans PubMed pour trouver des articles pertinents concernant la pathogenèse, le diagnostic et le pronostic de la pelade par plaques. Message principal La pelade par plaques est une forme de perte pileuse auto-immune dont la prévalence durant une vie est d’environ 2 %. Des antécédents personnels ou familiaux de troubles auto-immuns concomitants, comme le vitiligo ou une maladie de la thyroïde, peuvent être observés dans un petit sous-groupe de patients. Le diagnostic peut souvent être posé de manière clinique en se fondant sur la perte de cheveux non cicatricielle et circulaire caractéristique, accompagnée de cheveux en « point d’exclamation » en périphérie chez ceux dont le problème en est aux premiers stades. Le diagnostic des cas plus complexes ou des présentations inhabituelles peut être facilité par une biopsie et un examen histologique. Le pronostic varie largement et de mauvais résultats sont associés à une apparition à un âge précoce, une perte importante, la variante ophiasis, des changements aux ongles, des antécédents familiaux ou des troubles auto-immuns concomitants. Conclusion La pelade par plaques est une forme auto-immune de perte de cheveux périodiquement observée en soins primaires. Les médecins de famille sont bien placés pour identifier la pelade par plaques, déterminer la gravité de la maladie et poser le diagnostic différentiel approprié. De plus, ils sont en mesure de renseigner leurs patients à propos de l’évolution clinique de la maladie ainsi que du pronostic général selon le sous-type de patients.

  16. La pelade par plaques

    PubMed Central

    Spano, Frank; Donovan, Jeff C.

    2015-01-01

    Résumé Objectif Présenter aux médecins de famille des renseignements de base pour faire comprendre les schémas thérapeutiques et les résultats des traitements pour la pelade par plaques, de même que les aider à identifier les patients pour qui une demande de consultation en dermatologie pourrait s’imposer. Sources des données Une recension a été effectuée dans PubMed pour trouver des articles pertinents concernant le traitement de la pelade par plaques. Message principal La pelade par plaques est une forme auto-immune de perte pileuse qui touche à la fois les enfants et les adultes. Même s’il n’y a pas de mortalité associée à la maladie, la morbidité découlant des effets psychologiques de la perte des cheveux peut être dévastatrice. Lorsque la pelade par plaques et le sous-type de la maladie sont identifiés, un schéma thérapeutique approprié peut être amorcé pour aider à arrêter la chute des cheveux et possiblement faire commencer la repousse. Les traitements de première intention sont la triamcinolone intralésionnelle avec des corticostéroïdes topiques ou du minoxidil ou les 2. Les médecins de famille peuvent prescrire ces traitements en toute sécurité et amorcer ces thérapies. Les cas plus avancés ou réfractaires pourraient avoir besoin de diphénylcyclopropénone topique ou d’anthraline topique. On peut traiter la perte de cils avec des analogues de la prostaglandine. Les personnes ayant subi une perte de cheveux abondante peuvent recourir à des options de camouflage ou à des prothèses capillaires. Il est important de surveiller les troubles psychiatriques en raison des effets psychologiques profonds de la perte de cheveux. Conclusion Les médecins de famille verront de nombreux patients qui perdent leurs cheveux. La reconnaissance de la pelade par plaques et la compréhension du processus pathologique sous-jacent permettent d’amorcer un schéma thérapeutique approprié. Les cas plus graves ou r

  17. Ag-catalysed cutting of multi-walled carbon nanotubes.

    PubMed

    La Torre, A; Rance, G A; Miners, S A; Herreros Lucas, C; Smith, E F; Fay, M W; Zoberbier, T; Giménez-López, M C; Kaiser, U; Brown, P D; Khlobystov, A N

    2016-04-29

    In this work, the cutting of carbon nanotubes is investigated using silver nanoparticles deposited on arc discharge multi-walled carbon nanotubes. The composite is subsequently heated in air to fabricate shortened multi-walled nanotubes. Complementary transmission electron microscopy and spectroscopy techniques shed light on the cutting mechanism. The nanotube cutting is catalysed by the fundamental mechanism based on the coordination of the silver atoms to the π-bonds of carbon nanotubes. As a result of the metal coordination, the strength of the carbon-carbon bond is reduced, promoting the oxidation of carbon at lower temperature when heated in air, or lowering the activation energy required for the removal of carbon atoms by electron beam irradiation, assuring in both cases the cutting of the nanotubes.

  18. Ag-catalysed cutting of multi-walled carbon nanotubes

    NASA Astrophysics Data System (ADS)

    La Torre, A.; Rance, G. A.; Miners, S. A.; Herreros Lucas, C.; Smith, E. F.; Fay, M. W.; Zoberbier, T.; Giménez-López, M. C.; Kaiser, U.; Brown, P. D.; Khlobystov, A. N.

    2016-04-01

    In this work, the cutting of carbon nanotubes is investigated using silver nanoparticles deposited on arc discharge multi-walled carbon nanotubes. The composite is subsequently heated in air to fabricate shortened multi-walled nanotubes. Complementary transmission electron microscopy and spectroscopy techniques shed light on the cutting mechanism. The nanotube cutting is catalysed by the fundamental mechanism based on the coordination of the silver atoms to the π-bonds of carbon nanotubes. As a result of the metal coordination, the strength of the carbon-carbon bond is reduced, promoting the oxidation of carbon at lower temperature when heated in air, or lowering the activation energy required for the removal of carbon atoms by electron beam irradiation, assuring in both cases the cutting of the nanotubes.

  19. Carbon–heteroatom bond formation catalysed by organometallic complexes

    PubMed Central

    Hartwig, John F.

    2010-01-01

    At one time the synthetic chemist’s last resort, reactions catalysed by transition metals are now the preferred method for synthesizing many types of organic molecule. A recent success in this type of catalysis is the discovery of reactions that form bonds between carbon and heteroatoms (such as nitrogen, oxygen, sulphur, silicon and boron) via complexes of transition metals with amides, alkoxides, thiolates, silyl groups or boryl groups. The development of these catalytic processes has been supported by the discovery of new elementary reactions that occur at metal–heteroatom bonds and by the identification of factors that control these reactions. Together, these findings have led to new synthetic processes that are in daily use and have formed a foundation for the development of processes that are likely to be central to synthetic chemistry in the future. PMID:18800130

  20. Phase-transfer-catalysed asymmetric synthesis of tetrasubstituted allenes

    NASA Astrophysics Data System (ADS)

    Hashimoto, Takuya; Sakata, Kazuki; Tamakuni, Fumiko; Dutton, Mark J.; Maruoka, Keiji

    2013-03-01

    Allenes are molecules based on three carbons connected by two cumulated carbon-carbon double bonds. Given their axially chiral nature and unique reactivity, substituted allenes have a variety of applications in organic chemistry as key synthetic intermediates and directly as part of biologically active compounds. Although the demands for these motivated many endeavours to make axially chiral, substituted allenes by exercising asymmetric catalysis, the catalytic asymmetric synthesis of fully substituted ones (tetrasubstituted allenes) remained largely an unsolved issue. The fundamental obstacle to solving this conundrum is the lack of a simple synthetic transformation that provides tetrasubstituted allenes in the action of catalysis. We report herein a strategy to overcome this issue by the use of a phase-transfer-catalysed asymmetric functionalization of 1-alkylallene-1,3-dicarboxylates with N-arylsulfonyl imines and benzylic and allylic bromides.

  1. Minding Rachlin's Eliminative Materialism

    ERIC Educational Resources Information Center

    McDowell, J. J.

    2012-01-01

    Rachlin's teleological behaviorism eliminates the first-person ontology of conscious experience by identifying mental states with extended patterns of behavior, and thereby maintains the materialist ontology of science. An alternate view, informed by brain-based and externalist philosophies of mind, is shown also to maintain the materialist…

  2. Windmill tower shadow eliminator

    SciTech Connect

    Randolph, A.J.

    1984-04-17

    In a wind driven propeller system an airfoil support for the shaft of a propeller having an even number of blades extends above and below the shaft a distance at least equal to the blade length and pivots with the propeller into the wind for substantially eliminating tower shadow effects on the propeller.

  3. Elimination chemistry in asphalt

    SciTech Connect

    Boucher, J.L.; Ihsiung Wang; Martinez, D.F. )

    1990-07-01

    Elimination chemistry provides important information, not only about the chemical properties of asphalt, but also the chemical modification method of asphalt. The chemical reactions which use the natural abundance of radicals are important for free-radical halogenation reaction. Spectral data demonstrates the formation of halogenated asphalt. The utility of dehydrohalogenation modified asphalt is limited. However, the resulting dehydrohalogenation modified asphalt does produce a significant unsaturated intermediate, which can incorporate elastomeric polymers (and monomers) via condensation or addition process. The second chemical modification method is the Hofmann elimination reaction, which was performed by reaction of methyl iodide with asphalt, followed by treatment of base. Spectroscopic data shows that a methyl group attached to nitrogen or sulfur in asphalt after Hofmann elimination reaction. Physical data shows that the Hofmann elimination modification improved the quality of asphalt, such as low temperature susceptibility measured by PVN. The modified asphalt also studied by HP-GPC in order to correlate their physical properties. The result shows that the molecular size distribution has changed and reduced the amount of LMS. The amount of decreasing LMS is also dependent on the content of nitrogen and sulfur in asphalts.

  4. Modeling disease elimination.

    PubMed

    Somerville, Kevin; Francombe, Paula

    2005-01-01

    The effect of the elimination of mortality from heart disease and cancer was modelled mathematically to allow for the effect of other competing causes of death. The model allows for potential dependence between heart disease or cancer and other causes of death by using cupola functions, which analyse the individual risk itself and the dependence structure between causes of death by using correlation coefficients. As the strength of these risk associations is unknown, the study investigated both full positive and negative dependence and compared this with no dependence. Depending upon the degree and type of correlation assumed, positive or negative, the life expectancy at birth is increased by between 3 months and 6.5 years if cancer mortality was eliminated, and between 5 months and 7.5 years in the case of heart disease. In addition, estimates of these effects on life insurance premia can be made with the greatest reduction for women with the elimination of cancer mortality. These figures provide a range of improvements in life expectancy and the consequent effect on life insurance risk premium rates which elimination of either of these important diseases would produce.

  5. Minding Rachlin's Eliminative Materialism

    PubMed Central

    McDowell, J.J

    2012-01-01

    Rachlin's teleological behaviorism eliminates the first-person ontology of conscious experience by identifying mental states with extended patterns of behavior, and thereby maintains the materialist ontology of science. An alternate view, informed by brain-based and externalist philosophies of mind, is shown also to maintain the materialist ontology of science, but without eliminating the phenomenology of consciousness. This view implies that to be judged human, machines not only must exhibit complicated temporally structured patterns of behavior, but also must have first-person conscious experience. Although confirming machine sentience is likely to be problematic, extended contact with a machine that results in a person interacting with it as if it were conscious could reasonably lead to the conclusion that for all intents and purposes it is. PMID:22942531

  6. Minding Rachlin's eliminative materialism.

    PubMed

    McDowell, J J

    2012-01-01

    Rachlin's teleological behaviorism eliminates the first-person ontology of conscious experience by identifying mental states with extended patterns of behavior, and thereby maintains the materialist ontology of science. An alternate view, informed by brain-based and externalist philosophies of mind, is shown also to maintain the materialist ontology of science, but without eliminating the phenomenology of consciousness. This view implies that to be judged human, machines not only must exhibit complicated temporally structured patterns of behavior, but also must have first-person conscious experience. Although confirming machine sentience is likely to be problematic, extended contact with a machine that results in a person interacting with it as if it were conscious could reasonably lead to the conclusion that for all intents and purposes it is. PMID:22942531

  7. Metallaphotoredox-catalysed sp(3)-sp(3) cross-coupling of carboxylic acids with alkyl halides.

    PubMed

    Johnston, Craig P; Smith, Russell T; Allmendinger, Simon; MacMillan, David W C

    2016-08-18

    In the past 50 years, cross-coupling reactions mediated by transition metals have changed the way in which complex organic molecules are synthesized. The predictable and chemoselective nature of these transformations has led to their widespread adoption across many areas of chemical research. However, the construction of a bond between two sp(3)-hybridized carbon atoms, a fundamental unit of organic chemistry, remains an important yet elusive objective for engineering cross-coupling reactions. In comparison to related procedures with sp(2)-hybridized species, the development of methods for sp(3)-sp(3) bond formation via transition metal catalysis has been hampered historically by deleterious side-reactions, such as β-hydride elimination with palladium catalysis or the reluctance of alkyl halides to undergo oxidative addition. To address this issue, nickel-catalysed cross-coupling processes can be used to form sp(3)-sp(3) bonds that utilize organometallic nucleophiles and alkyl electrophiles. In particular, the coupling of alkyl halides with pre-generated organozinc, Grignard and organoborane species has been used to furnish diverse molecular structures. However, the manipulations required to produce these activated structures is inefficient, leading to poor step- and atom-economies. Moreover, the operational difficulties associated with making and using these reactive coupling partners, and preserving them through a synthetic sequence, has hindered their widespread adoption. A generically useful sp(3)-sp(3) coupling technology that uses bench-stable, native organic functional groups, without the need for pre-functionalization or substrate derivatization, would therefore be valuable. Here we demonstrate that the synergistic merger of photoredox and nickel catalysis enables the direct formation of sp(3)-sp(3) bonds using only simple carboxylic acids and alkyl halides as the nucleophilic and electrophilic coupling partners, respectively. This metallaphotoredox

  8. Metallaphotoredox-catalysed sp(3)-sp(3) cross-coupling of carboxylic acids with alkyl halides.

    PubMed

    Johnston, Craig P; Smith, Russell T; Allmendinger, Simon; MacMillan, David W C

    2016-08-18

    In the past 50 years, cross-coupling reactions mediated by transition metals have changed the way in which complex organic molecules are synthesized. The predictable and chemoselective nature of these transformations has led to their widespread adoption across many areas of chemical research. However, the construction of a bond between two sp(3)-hybridized carbon atoms, a fundamental unit of organic chemistry, remains an important yet elusive objective for engineering cross-coupling reactions. In comparison to related procedures with sp(2)-hybridized species, the development of methods for sp(3)-sp(3) bond formation via transition metal catalysis has been hampered historically by deleterious side-reactions, such as β-hydride elimination with palladium catalysis or the reluctance of alkyl halides to undergo oxidative addition. To address this issue, nickel-catalysed cross-coupling processes can be used to form sp(3)-sp(3) bonds that utilize organometallic nucleophiles and alkyl electrophiles. In particular, the coupling of alkyl halides with pre-generated organozinc, Grignard and organoborane species has been used to furnish diverse molecular structures. However, the manipulations required to produce these activated structures is inefficient, leading to poor step- and atom-economies. Moreover, the operational difficulties associated with making and using these reactive coupling partners, and preserving them through a synthetic sequence, has hindered their widespread adoption. A generically useful sp(3)-sp(3) coupling technology that uses bench-stable, native organic functional groups, without the need for pre-functionalization or substrate derivatization, would therefore be valuable. Here we demonstrate that the synergistic merger of photoredox and nickel catalysis enables the direct formation of sp(3)-sp(3) bonds using only simple carboxylic acids and alkyl halides as the nucleophilic and electrophilic coupling partners, respectively. This metallaphotoredox

  9. Multimetallic catalysed cross-coupling of aryl bromides with aryl triflates

    NASA Astrophysics Data System (ADS)

    Ackerman, Laura K. G.; Lovell, Matthew M.; Weix, Daniel J.

    2015-08-01

    The advent of transition-metal catalysed strategies for forming new carbon-carbon bonds has revolutionized the field of organic chemistry, enabling the efficient synthesis of ligands, materials, and biologically active molecules. In cases where a single metal fails to promote a selective or efficient transformation, the synergistic cooperation of two distinct catalysts--multimetallic catalysis--can be used instead. Many important reactions rely on multimetallic catalysis, such as the Wacker oxidation of olefins and the Sonogashira coupling of alkynes with aryl halides, but this approach has largely been limited to the use of metals with distinct reactivities, with only one metal catalyst undergoing oxidative addition. Here, we demonstrate that cooperativity between two group 10 metal catalysts--(bipyridine)nickel and (1,3-bis(diphenylphosphino)propane)palladium--enables a general cross-Ullmann reaction (the cross-coupling of two different aryl electrophiles). Our method couples aryl bromides with aryl triflates directly, eliminating the use of arylmetal reagents and avoiding the challenge of differentiating between multiple carbon-hydrogen bonds that is required for direct arylation methods. Selectivity can be achieved without an excess of either substrate and originates from the orthogonal reactivity of the two catalysts and the relative stability of the two arylmetal intermediates. While (1,3-bis(diphenylphosphino)propane)palladium reacts preferentially with aryl triflates to afford a persistent intermediate, (bipyridine)nickel reacts preferentially with aryl bromides to form a transient, reactive intermediate. Although each catalyst forms less than 5 per cent cross-coupled product in isolation, together they are able to achieve a yield of up to 94 per cent. Our results reveal a new method for the synthesis of biaryls, heteroaryls, and dienes, as well as a general mechanism for the selective transfer of ligands between two metal catalysts. We anticipate that this

  10. Metallaphotoredox-catalysed sp3-sp3 cross-coupling of carboxylic acids with alkyl halides

    NASA Astrophysics Data System (ADS)

    Johnston, Craig P.; Smith, Russell T.; Allmendinger, Simon; MacMillan, David W. C.

    2016-08-01

    In the past 50 years, cross-coupling reactions mediated by transition metals have changed the way in which complex organic molecules are synthesized. The predictable and chemoselective nature of these transformations has led to their widespread adoption across many areas of chemical research. However, the construction of a bond between two sp3-hybridized carbon atoms, a fundamental unit of organic chemistry, remains an important yet elusive objective for engineering cross-coupling reactions. In comparison to related procedures with sp2-hybridized species, the development of methods for sp3-sp3 bond formation via transition metal catalysis has been hampered historically by deleterious side-reactions, such as β-hydride elimination with palladium catalysis or the reluctance of alkyl halides to undergo oxidative addition. To address this issue, nickel-catalysed cross-coupling processes can be used to form sp3-sp3 bonds that utilize organometallic nucleophiles and alkyl electrophiles. In particular, the coupling of alkyl halides with pre-generated organozinc, Grignard and organoborane species has been used to furnish diverse molecular structures. However, the manipulations required to produce these activated structures is inefficient, leading to poor step- and atom-economies. Moreover, the operational difficulties associated with making and using these reactive coupling partners, and preserving them through a synthetic sequence, has hindered their widespread adoption. A generically useful sp3-sp3 coupling technology that uses bench-stable, native organic functional groups, without the need for pre-functionalization or substrate derivatization, would therefore be valuable. Here we demonstrate that the synergistic merger of photoredox and nickel catalysis enables the direct formation of sp3-sp3 bonds using only simple carboxylic acids and alkyl halides as the nucleophilic and electrophilic coupling partners, respectively. This metallaphotoredox protocol is suitable for

  11. Recent advances in N-heterocyclic carbene (NHC)-catalysed benzoin reactions

    PubMed Central

    Menon, Rajeev S; Biju, Akkattu T

    2016-01-01

    Summary N-Heterocyclic carbenes (NHCs) have emerged as a powerful class of organocatalysts that mediate a variety of organic transformations. The Benzoin reaction constitutes one of the earliest known carbon–carbon bond-forming reactions catalysed by NHCs. The rapid growth of NHC catalysis in general has resulted in the development of a variety of benzoin and benzoin-type reactions. An overview of such NHC-catalysed benzoin reactions is presented. PMID:27340440

  12. Copper-catalysed enantioselective stereodivergent synthesis of amino alcohols

    NASA Astrophysics Data System (ADS)

    Shi, Shi-Liang; Wong, Zackary L.; Buchwald, Stephen L.

    2016-04-01

    The chirality, or ‘handedness’, of a biologically active molecule can alter its physiological properties. Thus it is routine procedure in the drug discovery and development process to prepare and fully characterize all possible stereoisomers of a drug candidate for biological evaluation. Despite many advances in asymmetric synthesis, developing general and practical strategies for obtaining all possible stereoisomers of an organic compound that has multiple contiguous stereocentres remains a challenge. Here, we report a stereodivergent copper-based approach for the expeditious construction of amino alcohols with high levels of chemo-, regio-, diastereo- and enantioselectivity. Specifically, we synthesized these amino-alcohol products using sequential, copper-hydride-catalysed hydrosilylation and hydroamination of readily available enals and enones. This strategy provides a route to all possible stereoisomers of the amino-alcohol products, which contain up to three contiguous stereocentres. We leveraged catalyst control and stereospecificity simultaneously to attain exceptional control of the product stereochemistry. Beyond the immediate utility of this protocol, our strategy could inspire the development of methods that provide complete sets of stereoisomers for other valuable synthetic targets.

  13. KOH catalysed preparation of activated carbon aerogels for dye adsorption.

    PubMed

    Ling, Sie King; Tian, H Y; Wang, Shaobin; Rufford, Thomas; Zhu, Z H; Buckley, C E

    2011-05-01

    Organic carbon aerogels (CAs) were prepared by a sol-gel method from polymerisation of resorcinol, furfural, and hexamethylenetetramine catalysed by KOH at around pH 9 using ambient pressure drying. The effect of KOH in the sol-gel on CA synthesis was studied. It was found that addition of KOH prior to the sol-gel polymerisation process improved thermal stability of the gel, prevented the crystallinity of the gel to graphite, increased the microporosity of CA and promoted activation of CA. The CAs prepared using the KOH catalyst exhibited higher porosity than uncatalysed prepared samples. Activation in CO(2) at higher temperature also enhanced the porosity of CAs. Adsorption tests indicated that the CAs were effective for both basic and acid dye adsorption and the adsorption increased with increasing surface area and pore volume. The kinetic adsorption of dyes was diffusion control and could be described by the second-order kinetic model. The equilibrium adsorption of dyes was higher than activated carbon. PMID:21345448

  14. Par Pond vegetation status 1996

    SciTech Connect

    Mackey, H.E. Jr.; Riley, R.S.

    1996-12-01

    The water level of Par Pond was lowered approximately 20 feet in mid-1991 in order to protect downstream residents from possible dam failure suggested by subsidence on the downstream slope of the dam and to repair the dam. This lowering exposed both emergent and nonemergent macrophyte beds to drying conditions resulting in extensive losses. A survey of the newly emergent, shoreline aquatic plant communities of Par Pond began in June 1995, three months after the refilling of Par Pond to approximately 200 feet above mean sea level. These surveys continued in July, September, and late October, 1995, and into the early spring and late summer of 1996. Communities similar to the pre-drawdown, Par Pond aquatic plant communities continue to become re-established. Emergent beds of maidencane, lotus, waterlily, watershield, and Pontederia are extensive and well developed. Measures of percent cover, width of beds, and estimates of area of coverage with satellite data indicate regrowth within two years of from 40 to 60% of levels prior to the draw down. Cattail occurrence continued to increase during the summer of 1996, especially in the former warm arm of Par Pond, but large beds common to Par Pond prior to the draw down still have not formed. Lotus has invaded and occupies many of the areas formerly dominated by cattail beds. To track the continued development of macrophytes in Par Pond, future surveys through the summer and early fall of 1997, along with the evaluation of satellite data to map the extent of the macrophyte beds of Par Pond, are planned.

  15. Horseradish peroxidase-catalysed in situ-forming hydrogels for tissue-engineering applications.

    PubMed

    Bae, Jin Woo; Choi, Jong Hoon; Lee, Yunki; Park, Ki Dong

    2015-11-01

    In situ-forming hydrogels are an attractive class of implantable biomaterials that are used for biomedical applications. These injectable hydrogels are versatile and provide a convenient platform for delivering cells and drugs via minimally invasive surgery. Although several crosslinking methods for preparing in situ forming hydrogels have been developed over the past two decades, most hydrogels are not sufficiently versatile for use in a wide variety of tissue-engineering applications. In recent years, enzyme-catalysed crosslinking approaches have been emerged as a new approach for developing in situ-forming hydrogels. In particular, the horseradish peroxidase (HRP)-catalysed crosslinking approach has received increasing interest, due to its highly improved and tunable capacity to obtain hydrogels with desirable properties. The HRP-catalysed crosslinking reaction immediately occurs upon mixing phenol-rich polymers with HRP and hydrogen peroxide (H2O2) in aqueous media. Based on this unique gel-forming feature, recent studies have shown that various properties of formed hydrogels, such as gelation time, stiffness and degradation rate, can be easily manipulated by varying the concentrations of HRP and H2O2. In this review, we outline the versatile properties of HRP-catalysed in situ-forming hydrogels, with a brief introduction to the crosslinking mechanisms involved. In addition, the recent biomedical applications of HRP-catalysed in situ-forming hydrogels for tissue regeneration are described. PMID:24916126

  16. Horseradish peroxidase-catalysed in situ-forming hydrogels for tissue-engineering applications.

    PubMed

    Bae, Jin Woo; Choi, Jong Hoon; Lee, Yunki; Park, Ki Dong

    2015-11-01

    In situ-forming hydrogels are an attractive class of implantable biomaterials that are used for biomedical applications. These injectable hydrogels are versatile and provide a convenient platform for delivering cells and drugs via minimally invasive surgery. Although several crosslinking methods for preparing in situ forming hydrogels have been developed over the past two decades, most hydrogels are not sufficiently versatile for use in a wide variety of tissue-engineering applications. In recent years, enzyme-catalysed crosslinking approaches have been emerged as a new approach for developing in situ-forming hydrogels. In particular, the horseradish peroxidase (HRP)-catalysed crosslinking approach has received increasing interest, due to its highly improved and tunable capacity to obtain hydrogels with desirable properties. The HRP-catalysed crosslinking reaction immediately occurs upon mixing phenol-rich polymers with HRP and hydrogen peroxide (H2O2) in aqueous media. Based on this unique gel-forming feature, recent studies have shown that various properties of formed hydrogels, such as gelation time, stiffness and degradation rate, can be easily manipulated by varying the concentrations of HRP and H2O2. In this review, we outline the versatile properties of HRP-catalysed in situ-forming hydrogels, with a brief introduction to the crosslinking mechanisms involved. In addition, the recent biomedical applications of HRP-catalysed in situ-forming hydrogels for tissue regeneration are described.

  17. 1,10-Phenanthroline as an accelerator for Ag nanoparticle-catalysed electroless copper deposition

    NASA Astrophysics Data System (ADS)

    Liu, Chia-Ru; Chou, Nan-Kuang; Li, Cheng-Hsing; Chen, Ho-Rei; Lee, Chien-Liang

    2014-10-01

    1,10-Phenanthroline (phen) can be successfully used as an accelerator for Ag-catalysed electroless copper deposition (ECD) processes. Electrochemical quartz crystal microbalance analyses indicate that the mass activity in terms of thickness of deposited Cu layer and average ECD rate within a deposition time of 110 s for Ag nanoparticles activated by phen are 7.86 × 10-3 μm μg-1 and 1.43 × 10-4 μm μg-1 s-1, respectively, whereas Ag nanoparticles without phen cannot catalyse the reaction. Furthermore, Tafel and cyclic voltammetric results show that the addition of phen to the ECD bath significantly enhances the ability of the Ag nanoparticles to catalyse the oxidation of HCHO and suppresses the formation of CuO.

  18. Eliminating Rabies in Estonia

    PubMed Central

    Cliquet, Florence; Robardet, Emmanuelle; Must, Kylli; Laine, Marjana; Peik, Katrin; Picard-Meyer, Evelyne; Guiot, Anne-Laure; Niin, Enel

    2012-01-01

    The compulsory vaccination of pets, the recommended vaccination of farm animals in grazing areas and the extermination of stray animals did not succeed in eliminating rabies in Estonia because the virus was maintained in two main wildlife reservoirs, foxes and raccoon dogs. These two species became a priority target therefore in order to control rabies. Supported by the European Community, successive oral vaccination (OV) campaigns were conducted twice a year using Rabigen® SAG2 baits, beginning in autumn 2005 in North Estonia. They were then extended to the whole territory from spring 2006. Following the vaccination campaigns, the incidence of rabies cases dramatically decreased, with 266 cases in 2005, 114 in 2006, four in 2007 and three in 2008. Since March 2008, no rabies cases have been detected in Estonia other than three cases reported in summer 2009 and one case in January 2011, all in areas close to the South-Eastern border with Russia. The bait uptake was satisfactory, with tetracycline positivity rates ranging from 85% to 93% in foxes and from 82% to 88% in raccoon dogs. Immunisation rates evaluated by ELISA ranged from 34% to 55% in foxes and from 38% to 55% in raccoon dogs. The rabies situation in Estonia was compared to that of the other two Baltic States, Latvia and Lithuania. Despite regular OV campaigns conducted throughout their territory since 2006, and an improvement in the epidemiological situation, rabies has still not been eradicated in these countries. An analysis of the number of baits distributed and the funding allocated by the European Commission showed that the strategy for rabies control is more cost-effective in Estonia than in Latvia and Lithuania. PMID:22393461

  19. USA supports measles elimination.

    PubMed

    1996-06-01

    The United States, through the United States Agency for International Development (USAID), has approved an $8 million grant in support of the Pan American Health Organization (PAHO) goal to eliminate measles in the Americas by the year 2000. From 1996 to 2001, the grant will complement regional efforts to stop the disease. Mrs. Hillary Clinton had pledged the support on World Health Day 1995. Although record low levels of measles cases were reported in 1995 for the region, the virus could be imported from elsewhere in the world. A major obstacle is the accumulation of susceptible preschool-aged children. As the proportion of susceptibles expands, the risk of a measles outbreak increases, if the virus is reintroduced. To prevent this, follow-up campaigns are being conducted throughout the region, focusing on all children aged 1-4 years, regardless of previous vaccination or disease history. PAHO recommends follow-up whenever the number of susceptible preschool children approaches the size of an average birth cohort. The interval between these campaigns and the specific age group targeted will depend on the vaccination coverage obtained through routine services since the last campaign. Follow-up campaigns were conducted in Cuba in 1993; in Belize, Brazil, Columbia, and Jamaica in 1995; and in Chile and the countries of Central America during April 1996. 19 million children were reached. Follow-up campaigns are planned for the remaining countries of the English-speaking Caribbean later in 1996. USAID played a key role in the successful completion of the 1994 poliomyelitis eradication initiative; the agency contributed approximately 60% of the external costs associated with the hemispheric campaign.

  20. USA supports measles elimination.

    PubMed

    1996-06-01

    The United States, through the United States Agency for International Development (USAID), has approved an $8 million grant in support of the Pan American Health Organization (PAHO) goal to eliminate measles in the Americas by the year 2000. From 1996 to 2001, the grant will complement regional efforts to stop the disease. Mrs. Hillary Clinton had pledged the support on World Health Day 1995. Although record low levels of measles cases were reported in 1995 for the region, the virus could be imported from elsewhere in the world. A major obstacle is the accumulation of susceptible preschool-aged children. As the proportion of susceptibles expands, the risk of a measles outbreak increases, if the virus is reintroduced. To prevent this, follow-up campaigns are being conducted throughout the region, focusing on all children aged 1-4 years, regardless of previous vaccination or disease history. PAHO recommends follow-up whenever the number of susceptible preschool children approaches the size of an average birth cohort. The interval between these campaigns and the specific age group targeted will depend on the vaccination coverage obtained through routine services since the last campaign. Follow-up campaigns were conducted in Cuba in 1993; in Belize, Brazil, Columbia, and Jamaica in 1995; and in Chile and the countries of Central America during April 1996. 19 million children were reached. Follow-up campaigns are planned for the remaining countries of the English-speaking Caribbean later in 1996. USAID played a key role in the successful completion of the 1994 poliomyelitis eradication initiative; the agency contributed approximately 60% of the external costs associated with the hemispheric campaign. PMID:12347182

  1. Copper-catalysed azide-alkyne cycloadditions (CuAAC): an update.

    PubMed

    Haldón, Estela; Nicasio, M Carmen; Pérez, Pedro J

    2015-10-01

    The reactions of organic azides and alkynes catalysed by copper species represent the prototypical examples of click chemistry. The so-called CuAAC reaction (copper-catalysed azide-alkyne cycloaddition), discovered in 2002, has been expanded since then to become an excellent tool in organic synthesis. In this contribution the recent results described in the literature since 2010 are reviewed, classified according to the nature of the catalyst precursor: copper(I) or copper(II) salts or complexes, metallic or nano-particulated copper and several solid-supported copper systems.

  2. Copper-catalysed azide-alkyne cycloadditions (CuAAC): an update.

    PubMed

    Haldón, Estela; Nicasio, M Carmen; Pérez, Pedro J

    2015-10-01

    The reactions of organic azides and alkynes catalysed by copper species represent the prototypical examples of click chemistry. The so-called CuAAC reaction (copper-catalysed azide-alkyne cycloaddition), discovered in 2002, has been expanded since then to become an excellent tool in organic synthesis. In this contribution the recent results described in the literature since 2010 are reviewed, classified according to the nature of the catalyst precursor: copper(I) or copper(II) salts or complexes, metallic or nano-particulated copper and several solid-supported copper systems. PMID:26284434

  3. Rhenium-catalysed dehydrogenative borylation of primary and secondary C(sp3)-H bonds adjacent to a nitrogen atom.

    PubMed

    Murai, Masahito; Omura, Tetsuya; Kuninobu, Yoichiro; Takai, Kazuhiko

    2015-03-18

    Rhenium-catalysed C(sp(3))-H bond borylation in the absence of any oxidant, hydrogen acceptor, or external ligand, with the generation of H2 as the sole byproduct is described. The transformation, which represents a rare example of rhenium-catalysed C(sp(3))-H bond functionalisation, features high atom efficiency and simple reaction conditions. PMID:25688385

  4. Rhenium-catalysed dehydrogenative borylation of primary and secondary C(sp3)-H bonds adjacent to a nitrogen atom.

    PubMed

    Murai, Masahito; Omura, Tetsuya; Kuninobu, Yoichiro; Takai, Kazuhiko

    2015-03-18

    Rhenium-catalysed C(sp(3))-H bond borylation in the absence of any oxidant, hydrogen acceptor, or external ligand, with the generation of H2 as the sole byproduct is described. The transformation, which represents a rare example of rhenium-catalysed C(sp(3))-H bond functionalisation, features high atom efficiency and simple reaction conditions.

  5. Operational Principles for the Dynamics of the In Vitro ParA-ParB System

    PubMed Central

    Jindal, Lavisha; Emberly, Eldon

    2015-01-01

    In many bacteria the ParA-ParB protein system is responsible for actively segregating DNA during replication. ParB proteins move by interacting with DNA bound ParA-ATP, stimulating their unbinding by catalyzing hydrolysis, that leads to rectified motion due to the creation of a wake of depleted ParA. Recent in vitro experiments have shown that a ParB covered magnetic bead can move with constant speed over a DNA covered substrate that is bound by ParA. It has been suggested that the formation of a gradient in ParA leads to diffusion-ratchet like motion of the ParB bead but how it forms and generates a force is still a matter of exploration. Here we develop a deterministic model for the in vitro ParA-ParB system and show that a ParA gradient can spontaneously form due to any amount of initial spatial noise in bound ParA. The speed of the bead is independent of this noise but depends on the ratio of the range of ParA-ParB force on the bead to that of removal of surface bound ParA by ParB. We find that at a particular ratio the speed attains a maximal value. We also consider ParA rebinding (including cooperativity) and ParA surface diffusion independently as mechanisms for ParA recovery on the surface. Depending on whether the DNA covered surface is undersaturated or saturated with ParA, we find that the bead can accelerate persistently or potentially stall. Our model highlights key requirements of the ParA-ParB driving force that are necessary for directed motion in the in vitro system that may provide insight into the in vivo dynamics of the ParA-ParB system. PMID:26670738

  6. Structure sensitivity in the nonscalable regime explored via catalysed ethylene hydrogenation on supported platinum nanoclusters.

    PubMed

    Crampton, Andrew S; Rötzer, Marian D; Ridge, Claron J; Schweinberger, Florian F; Heiz, Ueli; Yoon, Bokwon; Landman, Uzi

    2016-01-01

    The sensitivity, or insensitivity, of catalysed reactions to catalyst structure is a commonly employed fundamental concept. Here we report on the nature of nano-catalysed ethylene hydrogenation, investigated through experiments on size-selected Ptn (n=8-15) clusters soft-landed on magnesia and first-principles simulations, yielding benchmark information about the validity of structure sensitivity/insensitivity at the bottom of the catalyst size range. Both ethylene-hydrogenation-to-ethane and the parallel hydrogenation-dehydrogenation ethylidyne-producing route are considered, uncovering that at the <1 nm size-scale the reaction exhibits characteristics consistent with structure sensitivity, in contrast to structure insensitivity found for larger particles. The onset of catalysed hydrogenation occurs for Ptn (n ≥ 10) clusters at T>150 K, with maximum room temperature reactivity observed for Pt13. Structure insensitivity, inherent for specific cluster sizes, is induced in the more active Pt13 by a temperature increase up to 400 K leading to ethylidyne formation. Control of sub-nanometre particle size may be used for tuning catalysed hydrogenation activity and selectivity. PMID:26817713

  7. Ancillary ligand-free copper catalysed hydrohydrazination of terminal alkynes with NH2NH2.

    PubMed

    Peltier, Jesse L; Jazzar, Rodolphe; Melaimi, Mohand; Bertrand, Guy

    2016-02-14

    An efficient and selective Cu-catalysed hydrohydrazination of terminal alkynes with parent hydrazine is reported. The methodology tolerates a broad range of functional groups, allows for the synthesis of symmetrical and unsymmetrical azines, and can be extended to hydrazine derivatives and amines. PMID:26757745

  8. Room-Temperature Gold-Catalysed Arylation of Heteroarenes: Complementarity to Palladium Catalysis.

    PubMed

    Cresswell, Alexander J; Lloyd-Jones, Guy C

    2016-08-26

    Tailoring of the pre-catalyst, the oxidant and the arylsilane enables the first room-temperature, gold-catalysed, innate C-H arylation of heteroarenes. Regioselectivity is consistently high and, in some cases, distinct from that reported with palladium catalysis. Tolerance to halides and boronic esters, in both the heteroarene and silane partners, provides orthogonality to Suzuki-Miyaura coupling. PMID:27325239

  9. Structure sensitivity in the nonscalable regime explored via catalysed ethylene hydrogenation on supported platinum nanoclusters

    DOE PAGES

    Crampton, Andrew S.; Rötzer, Marian D.; Ridge, Claron J.; Schweinberger, Florian F.; Heiz, Ueli; Yoon, Bokwon; Landman, Uzi

    2016-01-28

    The sensitivity, or insensitivity, of catalysed reactions to catalyst structure is a commonly employed fundamental concept. Here we report on the nature of nano-catalysed ethylene hydrogenation, investigated through experiments on size-selected Ptn (n=8-15) clusters soft-landed on magnesia and first-principles simulations, yielding benchmark information about the validity of structure sensitivity/insensitivity at the bottom of the catalyst size range. Both ethylene-hydrogenation-to-ethane and the parallel hydrogenation–dehydrogenation ethylidyne-producing route are considered, uncovering that at the <1 nm size-scale the reaction exhibits characteristics consistent with structure sensitivity, in contrast to structure insensitivity found for larger particles. The onset of catalysed hydrogenation occurs for Ptn (n≥10)more » clusters at T>150 K, with maximum room temperature reactivity observed for Pt13. Structure insensitivity, inherent for specific cluster sizes, is induced in the more active Pt13 by a temperature increase up to 400 K leading to ethylidyne formation. As a result, control of sub-nanometre particle size may be used for tuning catalysed hydrogenation activity and selectivity.« less

  10. Catalytic and asymmetric cyclopropanation of alkenes catalysed by rhenium(I) bipyridine and terpyridine tricarbonyl complexes.

    PubMed

    Yeung, Chi-Tung; Teng, Pang-Fei; Yeung, Ho-Lun; Wong, Wing-Tak; Kwong, Hoi-Lun

    2007-12-01

    Re(I) tricarbonyl bipyridine and terpyridine complexes catalyse stereospecific cyclopropanation of alkenes; high selectivity of cyclopropane vs coupling and an ee of 73% and 62% for cis- and trans-cyclopropanes of styrene respectively were achieved with the [Re(L)(CO)(3)(MeCN)]OTf complex (L = chiral C(2)-symmetric terpyridine ligand).

  11. Structure sensitivity in the nonscalable regime explored via catalysed ethylene hydrogenation on supported platinum nanoclusters

    PubMed Central

    Crampton, Andrew S.; Rötzer, Marian D.; Ridge, Claron J.; Schweinberger, Florian F.; Heiz, Ueli; Yoon, Bokwon; Landman, Uzi

    2016-01-01

    The sensitivity, or insensitivity, of catalysed reactions to catalyst structure is a commonly employed fundamental concept. Here we report on the nature of nano-catalysed ethylene hydrogenation, investigated through experiments on size-selected Ptn (n=8–15) clusters soft-landed on magnesia and first-principles simulations, yielding benchmark information about the validity of structure sensitivity/insensitivity at the bottom of the catalyst size range. Both ethylene-hydrogenation-to-ethane and the parallel hydrogenation–dehydrogenation ethylidyne-producing route are considered, uncovering that at the <1 nm size-scale the reaction exhibits characteristics consistent with structure sensitivity, in contrast to structure insensitivity found for larger particles. The onset of catalysed hydrogenation occurs for Ptn (n≥10) clusters at T>150 K, with maximum room temperature reactivity observed for Pt13. Structure insensitivity, inherent for specific cluster sizes, is induced in the more active Pt13 by a temperature increase up to 400 K leading to ethylidyne formation. Control of sub-nanometre particle size may be used for tuning catalysed hydrogenation activity and selectivity. PMID:26817713

  12. Room-Temperature Gold-Catalysed Arylation of Heteroarenes: Complementarity to Palladium Catalysis.

    PubMed

    Cresswell, Alexander J; Lloyd-Jones, Guy C

    2016-08-26

    Tailoring of the pre-catalyst, the oxidant and the arylsilane enables the first room-temperature, gold-catalysed, innate C-H arylation of heteroarenes. Regioselectivity is consistently high and, in some cases, distinct from that reported with palladium catalysis. Tolerance to halides and boronic esters, in both the heteroarene and silane partners, provides orthogonality to Suzuki-Miyaura coupling.

  13. Par Pond Fish, Water, and Sediment Chemistry

    SciTech Connect

    Paller, M.H.; Wike, L.D.

    1996-06-01

    The objectives of this report are to describe the Par Pond fish community and the impact of the drawdown and refill on the community, describe contaminant levels in Par Pond fish, sediments, and water and indicate how contaminant concentrations and distributions were affected by the drawdown and refill, and predict possible effects of future water level fluctuations in Par Pond.

  14. Digoxin elimination by exchange transfusion.

    PubMed

    Rosegger, H; Zach, M; Gleispach, H; Beitzke, A

    1977-02-21

    The report covers four cases presenting simultaneous indications for digitalisation and exchange transfusions. Intravenous administration of digoxin was followed: 1. by monitoring of the behaviour of the plasma digoxin level; 2. by determination of the total amount of glycoside eliminated by the blood exchange. Particular attention was paid to the effect of the delay between injection and exchange transfusion on the amount of digoxin eliminated. All four cases showed moderate falls in plasma levels. The amounts of digoxin eliminated by exchange transfusion were in reverse relationship to the delay between administration of digoxin and the blood exchange. At no time did the eliminated fraction exceed 5% of the total amount present in the body. PMID:837948

  15. Directed and persistent movement arises from mechanochemistry of the ParA/ParB system

    NASA Astrophysics Data System (ADS)

    Hu, Longhua; Vecchiarelli, Anthony G.; Mizuuchi, Kiyoshi; Neuman, Keir C.; Liu, Jian

    The segregation of DNA prior to cell division is essential for faithful genetic inheritance. In many bacteria, segregation of the low-copy-number plasmids involves an active partition system composed of ParA ATPase and its stimulator protein ParB. Recent experiments suggest that ParA/ParB system motility is driven by a diffusion-ratchet mechanism in which ParB-coated plasmid both creates and follows a ParA gradient on the nucleoid surface. However, the detailed mechanism of ParA/ParB-mediated directed and persistent movement remains unknown. We develop a theoretical model describing ParA/ParB-mediated motility. We show that the ParA/ParB system can work as a Brownian ratchet, which effectively couples the ATPase-dependent cycling of ParA-nucleoid affinity to the motion of the ParB bound cargo. Paradoxically, the resulting processive motion relies on quenching diffusive plasmid motion through a large number of transient ParA/ParB-mediated tethers to the nucleoid surface. Our work sheds light on a new emergent phenomenon in which non-motor proteins work collectively via mechanochemical coupling to propel cargos -- an ingenious solution shaped by evolution to cope with the lack of processive motor proteins in bacteria.

  16. Parallel Climate Analysis Toolkit (ParCAT)

    SciTech Connect

    Smith, Brian Edward

    2013-06-30

    The parallel analysis toolkit (ParCAT) provides parallel statistical processing of large climate model simulation datasets. ParCAT provides parallel point-wise average calculations, frequency distributions, sum/differences of two datasets, and difference-of-average and average-of-difference for two datasets for arbitrary subsets of simulation time. ParCAT is a command-line utility that can be easily integrated in scripts or embedded in other application. ParCAT supports CMIP5 post-processed datasets as well as non-CMIP5 post-processed datasets. ParCAT reads and writes standard netCDF files.

  17. suPAR: The Molecular Crystal Ball

    PubMed Central

    Thunø, Maria; Macho, Betina; Eugen-Olsen, Jesper

    2009-01-01

    soluble urokinase Plasminogen Activator Receptor (suPAR) levels reflect inflammation and elevated suPAR levels are found in several infectious diseases and cancer. suPAR exists in three forms; suPARI-III, suPARII-III and suPARI which show different properties due to structural differences. Studies suggest that full-length suPAR is a regulator of uPAR/uPA by acting as uPA-scavenger, whereas the cleaved suPARII-III act as a chemotactic agent promoting the immune response via the SRSRY sequence in the linker-region. This review focus on the various suPAR fragments and their involvement in inflammation and pathogenic processes. We focus on the molecular mechanisms of the suPAR fragments and the link to the inflammatory process, as this could lead to medical applications in infectious and pathological conditions. PMID:19893210

  18. Measles - The epidemiology of elimination.

    PubMed

    Durrheim, David N; Crowcroft, Natasha S; Strebel, Peter M

    2014-12-01

    Tremendous progress has been made globally to reduce the contribution of measles to the burden of childhood deaths and measles cases have dramatically decreased with increased two dose measles-containing vaccine coverage. As a result the Global Vaccine Action Plan, endorsed by the World Health Assembly, has targeted measles elimination in at least five of the six World Health Organisation Regions by 2020. This is an ambitious goal, since measles control requires the highest immunisation coverage of any vaccine preventable disease, which means that the health system must be able to reach every community. Further, while measles remains endemic in any country, importations will result in local transmission and outbreaks in countries and Regions that have interrupted local endemic measles circulation. One of the lines of evidence that countries and Regions must address to confirm measles elimination is a detailed description of measles epidemiology over an extended period. This information is incredibly valuable as predictable epidemiological patterns emerge as measles elimination is approached and achieved. These critical features, including the source, size and duration of outbreaks, the seasonality and age-distribution of cases, genotyping pointers and effective reproduction rate estimates, are discussed with illustrative examples from the Region of the Americas, which eliminated measles in 2002, and the Western Pacific Region, which has established a Regional Verification Commission to review progress towards elimination in all member countries. PMID:25444814

  19. Measles - The epidemiology of elimination.

    PubMed

    Durrheim, David N; Crowcroft, Natasha S; Strebel, Peter M

    2014-12-01

    Tremendous progress has been made globally to reduce the contribution of measles to the burden of childhood deaths and measles cases have dramatically decreased with increased two dose measles-containing vaccine coverage. As a result the Global Vaccine Action Plan, endorsed by the World Health Assembly, has targeted measles elimination in at least five of the six World Health Organisation Regions by 2020. This is an ambitious goal, since measles control requires the highest immunisation coverage of any vaccine preventable disease, which means that the health system must be able to reach every community. Further, while measles remains endemic in any country, importations will result in local transmission and outbreaks in countries and Regions that have interrupted local endemic measles circulation. One of the lines of evidence that countries and Regions must address to confirm measles elimination is a detailed description of measles epidemiology over an extended period. This information is incredibly valuable as predictable epidemiological patterns emerge as measles elimination is approached and achieved. These critical features, including the source, size and duration of outbreaks, the seasonality and age-distribution of cases, genotyping pointers and effective reproduction rate estimates, are discussed with illustrative examples from the Region of the Americas, which eliminated measles in 2002, and the Western Pacific Region, which has established a Regional Verification Commission to review progress towards elimination in all member countries.

  20. Malaria elimination: surveillance and response

    PubMed Central

    Bridges, Daniel J; Winters, Anna M; Hamer, Davidson H

    2012-01-01

    In the last decade, substantial progress has been made in reducing malaria-associated morbidity and mortality across the globe. Nevertheless, sustained malaria control is essential to continue this downward trend. In some countries, where aggressive malaria control has reduced malaria to a low burden level, elimination, either nationally or subnationally, is now the aim. As countries or areas with a low malaria burden move towards elimination, there is a transition away from programs of universal coverage towards a strategy of localized detection and response to individual malaria cases. To do so and succeed, it is imperative that a strong surveillance and response system is supported, that community cadres are trained to provide appropriate diagnostics and treatment, and that field diagnostics are further developed such that their sensitivity allows for the detection and subsequent treatment of malaria reservoirs in low prevalence environments. To be certain, there are big challenges on the road to elimination, notably the development of drug and insecticide resistance. Nevertheless, countries like Zambia are making great strides towards implementing systems that support malaria elimination in target areas. Continued development of new diagnostics and antimalarial therapies is needed to support progress in malaria control and elimination. PMID:23265423

  1. Iron-catalysed cross-coupling of organolithium compounds with organic halides

    PubMed Central

    Jia, Zhenhua; Liu, Qiang; Peng, Xiao-Shui; Wong, Henry N. C.

    2016-01-01

    In past decades, catalytic cross-coupling reactions between organic halides and organometallic reagents to construct carbon–carbon bond have achieved a tremendous progress. However, organolithium reagents have rarely been used in cross-coupling reactions, due mainly to their high reactivity. Another limitation of this transformation using organolithium reagents is how to control reactivity with excellent selectivity. Although palladium catalysis has been applied in this field recently, the development of an approach to replace catalytic systems of noble metals with nonprecious metals is currently in high demand. Herein, we report an efficient synthetic protocol involving iron-catalysed cross-coupling reactions employing organolithium compounds as key coupling partners to unite aryl, alkyl and benzyl fragments and also disclose an efficient iron-catalysed release-capture ethylene coupling with isopropyllithium. PMID:26847602

  2. Sequence-regulated vinyl copolymers by metal-catalysed step-growth radical polymerization.

    PubMed

    Satoh, Kotaro; Ozawa, Satoshi; Mizutani, Masato; Nagai, Kanji; Kamigaito, Masami

    2010-04-12

    Proteins and nucleic acids are sequence-regulated macromolecules with various properties originating from their perfectly sequenced primary structures. However, the sequence regulation of synthetic polymers, particularly vinyl polymers, has not been achieved and is one of the ultimate goals in polymer chemistry. In this study, we report a strategy to obtain sequence-regulated vinyl copolymers consisting of styrene, acrylate and vinyl chloride units using metal-catalysed step-growth radical polyaddition of designed monomers prepared from common vinyl monomer building blocks. Unprecedented ABCC-sequence-regulated copolymers with perfect vinyl chloride-styrene-acrylate-acrylate sequences were obtained by copper-catalysed step-growth radical polymerization of designed monomers possessing unconjugated C=C and reactive C-Cl bonds. This strategy may open a new route in the study of sequence-regulated synthetic polymers.

  3. A steric tethering approach enables palladium-catalysed C-H activation of primary amino alcohols.

    PubMed

    Calleja, Jonas; Pla, Daniel; Gorman, Timothy W; Domingo, Victoriano; Haffemayer, Benjamin; Gaunt, Matthew J

    2015-12-01

    Aliphatic primary amines are a class of chemical feedstock essential to the synthesis of higher-order nitrogen-containing molecules, commonly found in biologically active compounds and pharmaceutical agents. New methods for the construction of complex amines remain a continuous challenge to synthetic chemists. Here, we outline a general palladium-catalysed strategy for the functionalization of aliphatic C-H bonds within amino alcohols, an important class of small molecule. Central to this strategy is the temporary conversion of catalytically incompatible primary amino alcohols into hindered secondary amines that are capable of undergoing a sterically promoted palladium-catalysed C-H activation. Furthermore, a hydrogen bond between amine and catalyst intensifies interactions around the palladium and orients the aliphatic amine substituents in an ideal geometry for C-H activation. This catalytic method directly transforms simple, easily accessible amines into highly substituted, functionally concentrated and structurally diverse products, and can streamline the synthesis of biologically important amine-containing molecules.

  4. Alkene Cleavage Catalysed by Heme and Nonheme Enzymes: Reaction Mechanisms and Biocatalytic Applications

    PubMed Central

    Mutti, Francesco G.

    2012-01-01

    The oxidative cleavage of alkenes is classically performed by chemical methods, although they display several drawbacks. Ozonolysis requires harsh conditions (−78°C, for a safe process) and reducing reagents in a molar amount, whereas the use of poisonous heavy metals such as Cr, Os, or Ru as catalysts is additionally plagued by low yield and selectivity. Conversely, heme and nonheme enzymes can catalyse the oxidative alkene cleavage at ambient temperature and atmospheric pressure in an aqueous buffer, showing excellent chemo- and regioselectivities in certain cases. This paper focuses on the alkene cleavage catalysed by iron cofactor-dependent enzymes encompassing the reaction mechanisms (in case where it is known) and the application of these enzymes in biocatalysis. PMID:22811656

  5. A steric tethering approach enables palladium-catalysed C-H activation of primary amino alcohols

    NASA Astrophysics Data System (ADS)

    Calleja, Jonas; Pla, Daniel; Gorman, Timothy W.; Domingo, Victoriano; Haffemayer, Benjamin; Gaunt, Matthew J.

    2015-12-01

    Aliphatic primary amines are a class of chemical feedstock essential to the synthesis of higher-order nitrogen-containing molecules, commonly found in biologically active compounds and pharmaceutical agents. New methods for the construction of complex amines remain a continuous challenge to synthetic chemists. Here, we outline a general palladium-catalysed strategy for the functionalization of aliphatic C-H bonds within amino alcohols, an important class of small molecule. Central to this strategy is the temporary conversion of catalytically incompatible primary amino alcohols into hindered secondary amines that are capable of undergoing a sterically promoted palladium-catalysed C-H activation. Furthermore, a hydrogen bond between amine and catalyst intensifies interactions around the palladium and orients the aliphatic amine substituents in an ideal geometry for C-H activation. This catalytic method directly transforms simple, easily accessible amines into highly substituted, functionally concentrated and structurally diverse products, and can streamline the synthesis of biologically important amine-containing molecules.

  6. Novel synthesis of fused isoxazolidines via a palladium catalysed allene insertion-intramoleculer 1,3-dipolar cycloaddition cascade reaction.

    PubMed

    Aftab, Tajassas; Grigg, Ronald; Ladlow, Mark; Sridharan, Visuvanathar; Thornton-Pett, Mark

    2002-08-21

    A one pot, three component palladium catalysed allenation of aryl iodides, in combination with a nitrone cycloaddition, leads to formation of fused isoxazolidines, creating two rings, two stereocentres and one tetrasubstituted carbon centre.

  7. Enantioselective synthesis of 3-hydroxy oxindoles by ytterbium-catalysed decarboxylative addition of β-ketoacids to isatins.

    PubMed

    Duan, Zhiqiang; Han, Jianlin; Qian, Ping; Zhang, Zirui; Wang, Yi; Pan, Yi

    2013-10-14

    A ytterbium(III)-indapybox catalysed enantioselective decarboxylative addition reaction of β-ketoacids to isatins is described. The biologically important 3-hydroxy oxindoles were obtained in high yields and excellent enantioselectivities.

  8. Directed and persistent movement arises from mechanochemistry of the ParA/ParB system.

    PubMed

    Hu, Longhua; Vecchiarelli, Anthony G; Mizuuchi, Kiyoshi; Neuman, Keir C; Liu, Jian

    2015-12-22

    The segregation of DNA before cell division is essential for faithful genetic inheritance. In many bacteria, segregation of low-copy number plasmids involves an active partition system composed of a nonspecific DNA-binding ATPase, ParA, and its stimulator protein ParB. The ParA/ParB system drives directed and persistent movement of DNA cargo both in vivo and in vitro. Filament-based models akin to actin/microtubule-driven motility were proposed for plasmid segregation mediated by ParA. Recent experiments challenge this view and suggest that ParA/ParB system motility is driven by a diffusion ratchet mechanism in which ParB-coated plasmid both creates and follows a ParA gradient on the nucleoid surface. However, the detailed mechanism of ParA/ParB-mediated directed and persistent movement remains unknown. Here, we develop a theoretical model describing ParA/ParB-mediated motility. We show that the ParA/ParB system can work as a Brownian ratchet, which effectively couples the ATPase-dependent cycling of ParA-nucleoid affinity to the motion of the ParB-bound cargo. Paradoxically, this resulting processive motion relies on quenching diffusive plasmid motion through a large number of transient ParA/ParB-mediated tethers to the nucleoid surface. Our work thus sheds light on an emergent phenomenon in which nonmotor proteins work collectively via mechanochemical coupling to propel cargos-an ingenious solution shaped by evolution to cope with the lack of processive motor proteins in bacteria.

  9. Directed and persistent movement arises from mechanochemistry of the ParA/ParB system

    PubMed Central

    Hu, Longhua; Vecchiarelli, Anthony G.; Mizuuchi, Kiyoshi; Neuman, Keir C.; Liu, Jian

    2015-01-01

    The segregation of DNA before cell division is essential for faithful genetic inheritance. In many bacteria, segregation of low-copy number plasmids involves an active partition system composed of a nonspecific DNA-binding ATPase, ParA, and its stimulator protein ParB. The ParA/ParB system drives directed and persistent movement of DNA cargo both in vivo and in vitro. Filament-based models akin to actin/microtubule-driven motility were proposed for plasmid segregation mediated by ParA. Recent experiments challenge this view and suggest that ParA/ParB system motility is driven by a diffusion ratchet mechanism in which ParB-coated plasmid both creates and follows a ParA gradient on the nucleoid surface. However, the detailed mechanism of ParA/ParB-mediated directed and persistent movement remains unknown. Here, we develop a theoretical model describing ParA/ParB-mediated motility. We show that the ParA/ParB system can work as a Brownian ratchet, which effectively couples the ATPase-dependent cycling of ParA–nucleoid affinity to the motion of the ParB-bound cargo. Paradoxically, this resulting processive motion relies on quenching diffusive plasmid motion through a large number of transient ParA/ParB-mediated tethers to the nucleoid surface. Our work thus sheds light on an emergent phenomenon in which nonmotor proteins work collectively via mechanochemical coupling to propel cargos—an ingenious solution shaped by evolution to cope with the lack of processive motor proteins in bacteria. PMID:26647183

  10. Iron-catalysed homo- and copolymerisation of propylene: steric influence of bis(imino)pyridine ligands.

    PubMed

    Kawakami, Takafumi; Ito, Shingo; Nozaki, Kyoko

    2015-12-21

    A series of iron complexes bearing a bis(imino)pyridine ligand were synthesised and examined as precatalysts for homopolymerisation of propylene. The alkyl substituents attached to the aryl group on the imine nitrogen atoms significantly affected the catalytic activity and molecular weight of the obtained polypropylenes. Copolymerisation of propylene and various allyl comonomers catalysed by iron/bis(imino)pyridine was also investigated. PMID:26568384

  11. Nitrene transfer reactions catalysed by copper(I) complexes in ionic liquid using chloramine-T.

    PubMed

    Cano, Israel; Nicasio, M Carmen; Pérez, Pedro J

    2009-01-28

    The complex [Tpm(*,Br)Cu(NCMe)]BF4 (Tpm(*,Br) = HC(3,5-Me2-4-Br-pyrazolyl)3) catalyses the aziridination of alkenes and the amidation of cyclic ethers with chloramine-T as the nitrene source and the ionic liquid [bmim]PF6 as the reaction medium (bmim = 1-n-butyl-3-methylimidazolium). High conversions have been obtained over several cycles of catalyst recovery and reuse.

  12. Copper-catalysed intramolecular O-arylation: a simple and efficient method for benzoxazole synthesis.

    PubMed

    Wu, Fengtian; Zhang, Jie; Wei, Qianbing; Liu, Ping; Xie, Jianwei; Jiang, Haojie; Dai, Bin

    2014-12-21

    A wide range of 2-substituted benzoxazoles can be efficiently synthesized from N-(2-iodo-/bromo-phenyl)benzamides, and even the less reactive N-(2-chlorophenyl)benzamides, via Cu-catalysed intramolecular coupling cyclization reactions using methyl 2-methoxybenzoate as the ligand under mild reaction conditions. In addition, the benzoxazoles can be easily prepared from the primary amides coupling with o-dihalobenzenes in a single step.

  13. Bacterial dioxygenase- and monooxygenase-catalysed sulfoxidation of benzo[b]thiophenes.

    PubMed

    Boyd, Derek R; Sharma, Narain D; McMurray, Brian; Haughey, Simon A; Allen, Christopher C R; Hamilton, John T G; McRoberts, W Colin; O'Ferrall, Rory A More; Nikodinovic-Runic, Jasmina; Coulombel, Lydie A; O'Connor, Kevin E

    2012-01-28

    Asymmetric heteroatom oxidation of benzo[b]thiophenes to yield the corresponding sulfoxides was catalysed by toluene dioxygenase (TDO), naphthalene dioxygenase (NDO) and styrene monooxygenase (SMO) enzymes present in P. putida mutant and E. coli recombinant whole cells. TDO-catalysed oxidation yielded the relatively unstable benzo[b]thiophene sulfoxide; its dimerization, followed by dehydrogenation, resulted in the isolation of stable tetracyclic sulfoxides as minor products with cis-dihydrodiols being the dominant metabolites. SMO mainly catalysed the formation of enantioenriched benzo[b]thiophene sulfoxide and 2-methyl benzo[b]thiophene sulfoxides which racemized at ambient temperature. The barriers to pyramidal sulfur inversion of 2- and 3-methyl benzo[b]thiophene sulfoxide metabolites, obtained using TDO and NDO as biocatalysts, were found to be ca.: 25-27 kcal mol(-1). The absolute configurations of the benzo[b]thiophene sulfoxides were determined by ECD spectroscopy, X-ray crystallography and stereochemical correlation. A site-directed mutant E. coli strain containing an engineered form of NDO, was found to change the regioselectivity toward preferential oxidation of the thiophene ring rather than the benzene ring. PMID:22134441

  14. Enzyme-catalysed synthesis and reactions of benzene oxide/oxepine derivatives of methyl benzoates.

    PubMed

    Boyd, Derek R; Sharma, Narain D; Harrison, John S; Malone, John F; McRoberts, W Colin; Hamilton, John T G; Harper, David B

    2008-04-01

    A series of twelve benzoate esters was metabolised, by species of the Phellinus genus of wood-rotting fungi, to yield the corresponding benzyl alcohol derivatives and eight salicylates. The isolation of a stable oxepine metabolite, from methyl benzoate, allied to evidence of the migration and retention of a carbomethoxy group (the NIH Shift), during enzyme-catalysed ortho-hydroxylation of alkyl benzoates to form salicylates, is consistent with a mechanism involving an initial arene epoxidation step. This mechanism was confirmed by the isolation of a remarkably stable, optically active, substituted benzene oxide metabolite of methyl 2-(trifluoromethyl)benzoate, which slowly converted into the racemic form. The arene oxide was found to undergo a cycloaddition reaction with 4-phenyl-1,2,4-triazoline-3,5-dione to yield a crystalline cycloadduct whose structure and racemic nature was established by X-ray crystallography. The metabolite was also found to undergo some novel benzene oxide reactions, including epoxidation to give an anti-diepoxide, base-catalysed hydrolysis to form a trans-dihydrodiol and acid-catalysed aromatisation to yield a salicylate derivative via the NIH Shift of a carbomethoxy group.

  15. Protease-activated receptor-1 (PAR1) and PAR2 but not PAR4 mediate relaxations in lower esophageal sphincter.

    PubMed

    Huang, Shih-Che

    2007-07-01

    Protease-activated receptor-1 (PAR1), PAR2 and PAR4 activation can alter the gastrointestinal motility. To investigate effects mediated by PARs in the lower esophageal sphincter, we measured contraction or relaxation of transverse strips from the guinea-pig lower esophageal sphincter caused by PAR1 (TFLLR-NH2 and SFLLRN-NH2), PAR2 (SLIGKV-NH2 and SLIGRL-NH2) and PAR4 peptide agonists (GYPGKF-NH2, GYPGQV-NH2 and AYPGKF-NH2) as well as PAR protease activators (thrombin and trypsin). In resting lower esophageal sphincter strips, TFLLR-NH2 and SFLLRN-NH2 caused moderate concentration-dependent relaxation whereas thrombin did not cause any relaxation or contraction. Furthermore, in carbachol-contracted strips, TFLLR-NH2 and SFLLRN-NH2 caused marked whereas thrombin caused mild concentration-dependent relaxation. These indicate the existence of PAR1 mediating relaxation. Similarly, in resting lower esophageal sphincter strips, trypsin caused moderate concentration-dependent relaxation whereas SLIGRL-NH2 and SLIGKV-NH2 did not cause any relaxation or contraction. In addition, in carbachol-contracted strips, trypsin caused marked whereas SLIGRL-NH2 and SLIGKV-NH2 caused mild concentration-dependent relaxation. These indicate the existence of PAR2 mediating relaxation. The relaxant response of thrombin, TFLLR-NH2, trypsin and SLIGKV-NH2 was insensitive to atropine or tetrodotoxin, suggesting a direct effect. The relaxant response of trypsin was not affected by apamin, charybdotoxin, indomethacin and capsaicin but was attenuated by NG-nitro-L-arginine methyl ester, indicating involvement of NO. FSLLR-NH2, a PAR1 control peptide, and VKGILS-NH2, a PAR2 control peptide, as well as all three PAR4 peptide agonists, GYPGKF-NH2, GYPGQV-NH2 and AYPGKF-NH2, did not cause any relaxation or contraction. Taken together, these results demonstrate that PAR1 and PAR2 but not PAR4 mediate relaxations in the guinea-pig lower esophageal sphincter. PMID:17335921

  16. The feasibility of eliminating podoconiosis.

    PubMed

    Deribe, Kebede; Wanji, Samuel; Shafi, Oumer; M Tukahebwa, Edrida; Umulisa, Irenee; Molyneux, David H; Davey, Gail

    2015-10-01

    La podoconiose est une maladie inflammatoire provoquée par un contact prolongé avec des minéraux irritants présents dans le sol. Les principaux symptômes incluent un gonflement des membres inférieurs (lymphœdème) et une douleur aiguë. Cette maladie a d'importantes conséquences sociales et économiques, car elle entraîne stigmatisation et perte de productivité. Ces cinq dernières années ont été marquées par des progrès satisfaisants en matière de recherche sur la podoconiose et de contrôle de cette maladie. Combattre la pauvreté au niveau des foyers et développer des infrastructures routières, d'approvisionnement en eau et urbaines peut contribuer à réduire son incidence. Les méthodes de lutte contre la podoconiose incluent le port de chaussures, une bonne hygiène des pieds et des revêtements de sol. La prévention secondaire et la prévention tertiaire reposent sur la gestion de la morbidité liée aux lymphœdèmes et passent par l'hygiène des pieds, les soins des pieds, les soins des plaies, la compression, des exercices, l'élévation des jambes et le traitement des infections aigües. Certains pays où la podoconiose est endémique ont pris l'initiative de l'inclure dans leur plan national pour la lutte contre les maladies tropicales négligées et de multiplier les interventions contre cette maladie. Des actions de sensibilisation sont nécessaires en vue de la distribution de chaussures comme mesure sanitaire. Nous recommandons de préciser les définitions de cas et les objectifs d'élimination pour servir de point de départ à l'éradication de cette maladie.

  17. Cancer risks: Strategies for elimination

    SciTech Connect

    Bannasch, P.

    1987-01-01

    This book deals with the possibilities for identifying and eliminating cancer risk factors. The current state of knowledge on the detection, assessment and elimination of chemical, physical (radiation), and biological (viruses) risk factors are comprehensively presented in 15 contributions. Chemical risk factors resulting from smoking and environmental contamination are given special attention. The coverage of cancer risks by radiation includes some of the consequences of the Chernobyl disaster. Finally, the discussion of the possible risks that certain viruses hold for cancer in man is intended to further the development of vaccinations against these viral infections. The information is directed not only at specialists, but also at a wider interested audience. Its primary aim is to convey established findings that are already being used for cancer prevention. Furthermore, the book aims to promote more intense research in the field of primary cancer prevention. Contents: General aspects; chemical carcinogens: Risk assessment; chemical carcinogens: Primary prevention; physical carcinogens - Oncogenic viruses and subject index.

  18. Eliminating sexism in the classroom.

    PubMed

    Shellenbarger, T

    1993-01-01

    Sexism exists in many nursing classrooms without the teacher or students being aware of it. Speech patterns, written-communication, and pedagogical styles may contribute to sexism. Nurse educators need to take measures to identify and eliminate sexism from the classroom, because it subordinates and limits students. The classroom should promote gender-free situations that enhance and contribute to learning and advancement of all students.

  19. PAR for the Course: A Congruent Pedagogical Approach for a PAR Methods Class

    ERIC Educational Resources Information Center

    Hammond, Joyce D.; Hicks, Maria; Kalman, Rowenn; Miller, Jason

    2005-01-01

    In the past two years, three graduate students and a senior faculty member have co-taught a participatory action research (PAR) course to undergraduate and graduate students. In this article the co-teachers advocate a set of pedagogical principles and practices in a PAR-oriented classroom that establishes congruency with community PAR projects in…

  20. Par Pond vegetation status Summer 1995 -- Summary

    SciTech Connect

    Mackey, H.E. Jr.; Riley, R.S.

    1996-01-01

    The water level of Par Pond was lowered approximately 20 feet in mid-1991 in order to protect downstream residents from possible dam failure suggested by subsidence on the downstream slope of the dam and to repair the dam. This lowering exposed both emergent and nonemergent macrophyte beds to drying conditions resulting in extensive losses. A survey of the newly emergent, shoreline aquatic plant communities of Par Pond began in June 1995, three months after the refilling of Par Pond to approximately 200 feet above mean sea level. These surveys continued in July, September, and late October, 1995. Communities similar to the pre-drawdown, Par Pond aquatic plant communities are becoming re-established. Emergent beds of maidencane, lotus, waterlily, and watershield are extensive and well developed. Cattail occurrence continued to increase during the summer, but large beds common to Par Pond prior to the drawdown have not formed. Estimates from SPOT HRV, remote sensing satellite data indicated that as much as 120 hectares of emergent wetlands vegetation may have been present along the Par Pond shoreline by early October, 1995. To track the continued development of macrophytes in Par Pond, future surveys throughout 1996 and 1997, along with the continued evaluation of satellite data to map the areal extent of the macrophyte beds of Par Pond, are planned.

  1. Regioselectivity and Enantioselectivity in Nickel-Catalysed Reductive Coupling Reactions of Alkynes

    PubMed Central

    Moslin, Ryan M.; Miller-Moslin, Karen; Jamison, Timothy F.

    2011-01-01

    Nickel-catalysed reductive coupling reactions of alkynes have emerged as powerful synthetic tools for the selective preparation of functionalized alkenes. One of the greatest challenges associated with these transformations is control of regioselectivity. Recent work from our laboratory has provided an improved understanding of several of the factors governing regioselectivity in these reactions, and related studies have revealed that the reaction mechanism can differ substantially depending on the ligand employed. A discussion of stereoselective transformations and novel applications of nickel catalysis in coupling reactions of alkynes is also included. PMID:17971951

  2. Lipase-catalysed transesterification of soya bean oil for biodiesel production during continuous batch operation.

    PubMed

    Du, Wei; Xu, Yuanyuan; Liu, Dehua

    2003-10-01

    The effects of temperature, oil/alcohol molar ratio and by-product glycerol were studied during Lipozyme TL IM-catalysed continuous batch operation when short-chain alcohols were used as the acyl acceptor. In non-continuous batch operation, the optimal oil/alcohol ratio and temperature were 1:4 and 40-50 degrees C; however, during the continuous batch operation, the optimal oil/alcohol ratio and temperature were 1:1 and 30 degrees C; 95% of enzymic activity remained after 10 batches when isopropanol was adopted to remove by-product glycerol during repeated use of the lipase.

  3. Partial reversal of the acetaldehyde and butyraldehyde oxidation reactions catalysed by aldehyde dehydrogenases from sheep liver.

    PubMed Central

    Hart, G J; Dickinson, F M

    1978-01-01

    In the presence of acetic anhydride or butyric anhydride, liver aldehyde dehydrogenases catalyse the oxidation of NADH at pH 7.0 and 25 degrees C. The maximum velocities and Michaelis constants for NADH at saturating anhydride concentrations are independent of which anhydride is used, the values being V'max. = 12 min-1 and Km for NADH = 9 micrometer for the mitochondrial enzyme and V'max = 25 min-1 and Km for NADH = 20 micrometer for the cytoplasmic enzyme. Substitution of [4A-2H]NADH for NADH resulted in 2-fold and 4-fold decreases in rate for the mitochondrial and cytoplasmic enzymes respectively. PMID:217349

  4. Towards the elimination of onchocerciasis.

    PubMed

    Thylefors, B; Alleman, M

    2006-12-01

    Human onchocerciasis is a severely disabling filarial disease that is endemic in 28 African countries, six Latin American countries and Yemen. The disease causes a high burden of blindness and visual loss, along with itching and other severe dermal manifestations. It constitutes a significant obstacle to socio-economic development in highly endemic riverine areas, where the Simulium blackflies that act as vectors breed. Onchocerciasis has been subject to control efforts for more than 50 years, initially mainly through vector control but since 1988, with free access to ivermectin (Mectizan), also through large-scale chemotherapy. The Onchocerciasis Control Programme in West Africa operated successfully from 1974 to 2002 in 11 countries, covering the worst savannah foci of the disease through vector control and, in its later stages, also through ivermectin distribution. The African Programme for Onchocerciasis Control was established in 1995, to cover the remaining endemic areas in Africa, with the sustainable annual distribution of ivermectin by 2010 its main goal. Meanwhile, the Onchocerciasis Elimination Program for the Americas is making rapid progress in the virtual regional elimination of the disease through ivermectin distribution, which is achievable primarily because the vectors in the western hemisphere are less efficient than those elsewhere. The global elimination of onchocerciasis as a public-health problem is now within reach but this will require long-term strategies to secure the great gains made so far, through ivermectin treatment and local vector control. Research is needed to define the optimal approaches with the existing tools and to intensify the development of alternative strategies, such as macrofilaricidal drugs for wide-scale use. PMID:17227651

  5. Towards the elimination of onchocerciasis.

    PubMed

    Thylefors, B; Alleman, M

    2006-12-01

    Human onchocerciasis is a severely disabling filarial disease that is endemic in 28 African countries, six Latin American countries and Yemen. The disease causes a high burden of blindness and visual loss, along with itching and other severe dermal manifestations. It constitutes a significant obstacle to socio-economic development in highly endemic riverine areas, where the Simulium blackflies that act as vectors breed. Onchocerciasis has been subject to control efforts for more than 50 years, initially mainly through vector control but since 1988, with free access to ivermectin (Mectizan), also through large-scale chemotherapy. The Onchocerciasis Control Programme in West Africa operated successfully from 1974 to 2002 in 11 countries, covering the worst savannah foci of the disease through vector control and, in its later stages, also through ivermectin distribution. The African Programme for Onchocerciasis Control was established in 1995, to cover the remaining endemic areas in Africa, with the sustainable annual distribution of ivermectin by 2010 its main goal. Meanwhile, the Onchocerciasis Elimination Program for the Americas is making rapid progress in the virtual regional elimination of the disease through ivermectin distribution, which is achievable primarily because the vectors in the western hemisphere are less efficient than those elsewhere. The global elimination of onchocerciasis as a public-health problem is now within reach but this will require long-term strategies to secure the great gains made so far, through ivermectin treatment and local vector control. Research is needed to define the optimal approaches with the existing tools and to intensify the development of alternative strategies, such as macrofilaricidal drugs for wide-scale use.

  6. ParAB Partition Dynamics in Firmicutes: Nucleoid Bound ParA Captures and Tethers ParB-Plasmid Complexes

    PubMed Central

    Lioy, Virginia S.; Volante, Andrea; Soberón, Nora E.; Lurz, Rudi; Ayora, Silvia; Alonso, Juan C.

    2015-01-01

    In Firmicutes, small homodimeric ParA-like (δ2) and ParB-like (ω2) proteins, in concert with cis-acting plasmid-borne parS and the host chromosome, secure stable plasmid inheritance in a growing bacterial population. This study shows that (ω:YFP)2 binding to parS facilitates plasmid clustering in the cytosol. (δ:GFP)2 requires ATP binding but not hydrolysis to localize onto the cell’s nucleoid as a fluorescent cloud. The interaction of (δ:CFP)2 or δ2 bound to the nucleoid with (ω:YFP)2 foci facilitates plasmid capture, from a very broad distribution, towards the nucleoid and plasmid pairing. parS-bound ω2 promotes redistribution of (δ:GFP)2, leading to the dynamic release of (δ:GFP)2 from the nucleoid, in a process favored by ATP hydrolysis and protein-protein interaction. (δD60A:GFP)2, which binds but cannot hydrolyze ATP, also forms unstable complexes on the nucleoid. In the presence of ω2, (δD60A:GFP)2 accumulates foci or patched structures on the nucleoid. We propose that (δ:GFP)2 binding to different nucleoid regions and to ω2-parS might generate (δ:GFP)2 gradients that could direct plasmid movement. The iterative pairing and unpairing cycles may tether plasmids equidistantly on the nucleoid to ensure faithful plasmid segregation by a mechanism compatible with the diffusion-ratchet mechanism as proposed from in vitro reconstituted systems. PMID:26161642

  7. Effect of V/III ratio on the structural and optical properties of self-catalysed GaAs nanowires

    NASA Astrophysics Data System (ADS)

    Ahtapodov, L.; Munshi, A. M.; Nilsen, J. S.; Reinertsen, J. F.; Dheeraj, D. L.; Fimland, B. O.; van Helvoort, A. T. J.; Weman, H.

    2016-11-01

    The performance of GaAs nanowire (NW) devices depends critically on the presence of crystallographic defects in the NWs such as twinning planes and stacking faults, and considerable effort has been devoted to understanding and preventing the occurrence of these. For self-catalysed GaAs NWs grown by molecular beam epitaxy (MBE) in particular, there are in addition other types of defects that may be just as important for NW-based optoelectronic devices. These are the point defects such as the As vacancy and the Ga antisite occurring due to the inherently Ga-rich conditions of the self-catalysed growth. Here we demonstrate experimentally the effects of these point defects on the optical properties of GaAs/AlGaAs core–shell NWs grown by self-catalysed MBE. The present results enable insight into the role of the point defects both on their own and in conjunction with crystallographic planar defects.

  8. The feasibility of eliminating podoconiosis

    PubMed Central

    Wanji, Samuel; Shafi, Oumer; M Tukahebwa, Edrida; Umulisa, Irenee; Molyneux, David H; Davey, Gail

    2015-01-01

    Abstract Podoconiosis is an inflammatory disease caused by prolonged contact with irritant minerals in soil. Major symptoms include swelling of the lower limb (lymphoedema) and acute pain. The disease has major social and economic consequences through stigma and loss of productivity. In the last five years there has been good progress in podoconiosis research and control. Addressing poverty at household level and infrastructure development such as roads, water and urbanization can all help to reduce podoconiosis incidence. Specific control methods include the use of footwear, regular foot hygiene and floor coverings. Secondary and tertiary prevention are based on the management of the lymphoedema-related morbidity and include foot hygiene, foot care, wound care, compression, exercises, elevation of the legs and treatment of acute infections. Certain endemic countries are taking the initiative to include podoconiosis in their national plans for the control of neglected tropical diseases and to scale up interventions against the disease. Advocacy is needed for provision of shoes as a health intervention. We suggest case definitions and elimination targets as a starting point for elimination of the disease. PMID:26600613

  9. Non-stabilized nucleophiles in Cu-catalysed dynamic kinetic asymmetric allylic alkylation

    NASA Astrophysics Data System (ADS)

    You, Hengzhi; Rideau, Emeline; Sidera, Mireia; Fletcher, Stephen P.

    2015-01-01

    The development of new reactions forming asymmetric carbon-carbon bonds has enabled chemists to synthesize a broad range of important carbon-containing molecules, including pharmaceutical agents, fragrances and polymers. Most strategies to obtain enantiomerically enriched molecules rely on either generating new stereogenic centres from prochiral substrates or resolving racemic mixtures of enantiomers. An alternative strategy--dynamic kinetic asymmetric transformation--involves the transformation of a racemic starting material into a single enantiomer product, with greater than 50 per cent maximum yield. The use of stabilized nucleophiles (pKa < 25, where Ka is the acid dissociation constant) in palladium-catalysed asymmetric allylic alkylation reactions has proved to be extremely versatile in these processes. Conversely, the use of non-stabilized nucleophiles in such reactions is difficult and remains a key challenge. Here we report a copper-catalysed dynamic kinetic asymmetric transformation using racemic substrates and alkyl nucleophiles. These nucleophiles have a pKa of >=50, more than 25 orders of magnitude more basic than the nucleophiles that are typically used in such transformations. Organometallic reagents are generated in situ from alkenes by hydrometallation and give highly enantioenriched products under mild reaction conditions. The method is used to synthesize natural products that possess activity against tuberculosis and leprosy, and an inhibitor of para-aminobenzoate biosynthesis. Mechanistic studies indicate that the reaction proceeds through a rapidly isomerizing intermediate. We anticipate that this approach will be a valuable complement to existing asymmetric catalytic methods.

  10. Atomic scale observation of oxygen delivery during silver–oxygen nanoparticle catalysed oxidation of carbon nanotubes

    PubMed Central

    Yue, Yonghai; Yuchi, Datong; Guan, Pengfei; Xu, Jia; Guo, Lin; Liu, Jingyue

    2016-01-01

    To probe the nature of metal-catalysed processes and to design better metal-based catalysts, atomic scale understanding of catalytic processes is highly desirable. Here we use aberration-corrected environmental transmission electron microscopy to investigate the atomic scale processes of silver-based nanoparticles, which catalyse the oxidation of multi-wall carbon nanotubes. A direct semi-quantitative estimate of the oxidized carbon atoms by silver-based nanoparticles is achieved. A mechanism similar to the Mars–van Krevelen process is invoked to explain the catalytic oxidation process. Theoretical calculations, together with the experimental data, suggest that the oxygen molecules dissociate on the surface of silver nanoparticles and diffuse through the silver nanoparticles to reach the silver/carbon interfaces and subsequently oxidize the carbon. The lattice distortion caused by oxygen concentration gradient within the silver nanoparticles provides the direct evidence for oxygen diffusion. Such direct observation of atomic scale dynamics provides an important general methodology for investigations of catalytic processes. PMID:27406595

  11. Hydrolysis of hydrophobic esters in a bicontinuous microemulsion catalysed by lipase B from Candida antarctica.

    PubMed

    Steudle, Anne K; Subinya, Mireia; Nestl, Bettina M; Stubenrauch, Cosima

    2015-02-01

    Selective enzyme-catalysed biotransformations offer great potential in organic chemistry. However, special requirements are needed to achieve optimum enzyme activity and stability. A bicontinuous microemulsion is proposed as reaction medium because of its large connected interface between oil and water domains at which a lipase can adsorb and convert substrates in the oil phase of the microemulsion. Herein, a microemulsion consisting of buffer-n-octane-nonionic surfactant Ci Ej was used to investigate the key factors that determine hydrolyses of p-nitrophenyl esters catalysed by the lipase B from Candida antarctica (CalB). The highest CalB activity was found around 44 °C in the absence of NaCl and substrates with larger alkyl chains were better hydrolysed than their short-chained homologues. The CalB activity was determined using two different co-surfactants, namely the phospholipid 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC) and the sugar surfactant decyl β-D-glucopyranoside (β-C10 G1 ). The results show the CalB activity as linear function of both enzyme and substrate concentration with an enhanced activity when the sugar surfactant is used as co-surfactant.

  12. Palladium-catalysed norbornene-mediated C-H functionalization of arenes

    NASA Astrophysics Data System (ADS)

    Ye, Juntao; Lautens, Mark

    2015-11-01

    The Catellani reaction -- a palladium-catalysed C-H functionalization reaction mediated by norbornene -- was first reported in 1997. The capacity to functionalize both the ortho and ipso positions of aryl halides in a single transformation held great appeal. We reported an annulative Catellani reaction in 2000. Since then, our two groups have explored the synthetic utility of this reaction and dramatic progress has been made by a number of groups in the past five years. Whereas the original Catellani reaction uses Pd(0) catalysts, recent studies have shown that Pd(II) catalysts can be used in combination with norbornene to effect (1) direct 2-alkylation of indoles and pyrroles and (2) selective meta-C-H functionalization of arenes bearing commonly used ortho-directing groups, thereby opening new avenues for future research. We describe the most recent developments concerning the Pd-catalysed norbornene-mediated C-H functionalization of arenes, including applications in natural products synthesis. We outline challenges and future opportunities.

  13. Use of ESR and HPLC to follow the anaerobic reaction catalysed by lipoxygenases.

    PubMed

    Brandicourt, Stéphanie; Nicolas, Jacques; Boussard, Aline; Riquet, Anne-Marie

    2015-02-01

    The measurement of the 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPOL) consumption by using ESR allows to follow the anaerobic reaction between linoleic acid (LH) and its 13-hydroperoxide (LOOH) catalysed by lipoxygenase. During this reaction, two types of radicals are initially obtained, alkyl (L) and alkoxyl (LO) radicals which formed two types of adducts (LT and OLT) with TEMPOL as characterised by HPLC. The stoichiometry of the adduct formation is two mole of TEMPOL consumed for one mole of LH and one mole of LOOH. Using ESR, the kinetic parameters and the mechanism of the anaerobic reaction have been determined at pH 6.5 for three different lipoxygenases, soybean, horse bean and wheat and compared to the values obtained at pH 9 for soybean lipoxygenase. Wheat lipoxygenase is very weakly active compared to the other enzymes. An uncompetitive inhibition of the anaerobic reaction catalysed by soybean and horse bean lipoxygenases was observed with 2,6-di-tert-butyl-4-methylphenol (BHT).

  14. Atomic scale observation of oxygen delivery during silver-oxygen nanoparticle catalysed oxidation of carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Yue, Yonghai; Yuchi, Datong; Guan, Pengfei; Xu, Jia; Guo, Lin; Liu, Jingyue

    2016-07-01

    To probe the nature of metal-catalysed processes and to design better metal-based catalysts, atomic scale understanding of catalytic processes is highly desirable. Here we use aberration-corrected environmental transmission electron microscopy to investigate the atomic scale processes of silver-based nanoparticles, which catalyse the oxidation of multi-wall carbon nanotubes. A direct semi-quantitative estimate of the oxidized carbon atoms by silver-based nanoparticles is achieved. A mechanism similar to the Mars-van Krevelen process is invoked to explain the catalytic oxidation process. Theoretical calculations, together with the experimental data, suggest that the oxygen molecules dissociate on the surface of silver nanoparticles and diffuse through the silver nanoparticles to reach the silver/carbon interfaces and subsequently oxidize the carbon. The lattice distortion caused by oxygen concentration gradient within the silver nanoparticles provides the direct evidence for oxygen diffusion. Such direct observation of atomic scale dynamics provides an important general methodology for investigations of catalytic processes.

  15. Atomic scale observation of oxygen delivery during silver-oxygen nanoparticle catalysed oxidation of carbon nanotubes.

    PubMed

    Yue, Yonghai; Yuchi, Datong; Guan, Pengfei; Xu, Jia; Guo, Lin; Liu, Jingyue

    2016-07-13

    To probe the nature of metal-catalysed processes and to design better metal-based catalysts, atomic scale understanding of catalytic processes is highly desirable. Here we use aberration-corrected environmental transmission electron microscopy to investigate the atomic scale processes of silver-based nanoparticles, which catalyse the oxidation of multi-wall carbon nanotubes. A direct semi-quantitative estimate of the oxidized carbon atoms by silver-based nanoparticles is achieved. A mechanism similar to the Mars-van Krevelen process is invoked to explain the catalytic oxidation process. Theoretical calculations, together with the experimental data, suggest that the oxygen molecules dissociate on the surface of silver nanoparticles and diffuse through the silver nanoparticles to reach the silver/carbon interfaces and subsequently oxidize the carbon. The lattice distortion caused by oxygen concentration gradient within the silver nanoparticles provides the direct evidence for oxygen diffusion. Such direct observation of atomic scale dynamics provides an important general methodology for investigations of catalytic processes.

  16. F-O-G Ring Formation in Glycopeptide Antibiotic Biosynthesis is Catalysed by OxyE

    PubMed Central

    Peschke, Madeleine; Brieke, Clara; Cryle, Max J.

    2016-01-01

    The glycopeptide antibiotics are peptide-based natural products with impressive antibiotic function that derives from their unique three-dimensional structure. Biosynthesis of the glycopeptide antibiotics centres of the combination of peptide synthesis, mediated by a non-ribosomal peptide synthetase, and the crosslinking of aromatic side chains of the peptide, mediated by the action of a cascade of Cytochrome P450s. Here, we report the first example of in vitro activity of OxyE, which catalyses the F-O-G ring formation reaction in teicoplanin biosynthesis. OxyE was found to only act after an initial C-O-D crosslink is installed by OxyB and to require an interaction with the unique NRPS domain from glycopeptide antibiotic – the X-domain – in order to display catalytic activity. We could demonstrate that OxyE displays limited stereoselectivity for the peptide, which mirrors the results from OxyB-catalysed turnover and is in sharp contrast to OxyA. Furthermore, we show that activity of a three-enzyme cascade (OxyB/OxyA/OxyE) in generating tricyclic glycopeptide antibiotic peptides depends upon the order of addition of the OxyA and OxyE enzymes to the reaction. This work demonstrates that complex enzymatic cascades from glycopeptide antibiotic biosynthesis can be reconstituted in vitro and provides new insights into the biosynthesis of these important antibiotics. PMID:27752135

  17. Challenging nickel-catalysed amine arylations enabled by tailored ancillary ligand design

    PubMed Central

    Lavoie, Christopher M.; MacQueen, Preston M.; Rotta-Loria, Nicolas L.; Sawatzky, Ryan S.; Borzenko, Andrey; Chisholm, Alicia J.; Hargreaves, Breanna K. V.; McDonald, Robert; Ferguson, Michael J.; Stradiotto, Mark

    2016-01-01

    Palladium-catalysed C(sp2)–N cross-coupling (that is, Buchwald–Hartwig amination) is employed widely in synthetic chemistry, including in the pharmaceutical industry, for the synthesis of (hetero)aniline derivatives. However, the cost and relative scarcity of palladium provides motivation for the development of alternative, more Earth-abundant catalysts for such transformations. Here we disclose an operationally simple and air-stable ligand/nickel(II) pre-catalyst that accommodates the broadest combination of C(sp2)–N coupling partners reported to date for any single nickel catalyst, without the need for a precious-metal co-catalyst. Key to the unprecedented performance of this pre-catalyst is the application of the new, sterically demanding yet electron-poor bisphosphine PAd-DalPhos. Featured are the first reports of nickel-catalysed room temperature reactions involving challenging primary alkylamine and ammonia reaction partners employing an unprecedented scope of electrophiles, including transformations involving sought-after (hetero)aryl mesylates for which no capable catalyst system is known. PMID:27004442

  18. Atomic scale observation of oxygen delivery during silver-oxygen nanoparticle catalysed oxidation of carbon nanotubes.

    PubMed

    Yue, Yonghai; Yuchi, Datong; Guan, Pengfei; Xu, Jia; Guo, Lin; Liu, Jingyue

    2016-01-01

    To probe the nature of metal-catalysed processes and to design better metal-based catalysts, atomic scale understanding of catalytic processes is highly desirable. Here we use aberration-corrected environmental transmission electron microscopy to investigate the atomic scale processes of silver-based nanoparticles, which catalyse the oxidation of multi-wall carbon nanotubes. A direct semi-quantitative estimate of the oxidized carbon atoms by silver-based nanoparticles is achieved. A mechanism similar to the Mars-van Krevelen process is invoked to explain the catalytic oxidation process. Theoretical calculations, together with the experimental data, suggest that the oxygen molecules dissociate on the surface of silver nanoparticles and diffuse through the silver nanoparticles to reach the silver/carbon interfaces and subsequently oxidize the carbon. The lattice distortion caused by oxygen concentration gradient within the silver nanoparticles provides the direct evidence for oxygen diffusion. Such direct observation of atomic scale dynamics provides an important general methodology for investigations of catalytic processes. PMID:27406595

  19. Metallaphotoredox-catalysed sp3–sp3 cross-coupling of carboxylic acids with alkyl halides

    NASA Astrophysics Data System (ADS)

    Johnston, Craig P.; Smith, Russell T.; Allmendinger, Simon; MacMillan, David W. C.

    2016-08-01

    In the past 50 years, cross-coupling reactions mediated by transition metals have changed the way in which complex organic molecules are synthesized. The predictable and chemoselective nature of these transformations has led to their widespread adoption across many areas of chemical research. However, the construction of a bond between two sp3-hybridized carbon atoms, a fundamental unit of organic chemistry, remains an important yet elusive objective for engineering cross-coupling reactions. In comparison to related procedures with sp2-hybridized species, the development of methods for sp3–sp3 bond formation via transition metal catalysis has been hampered historically by deleterious side-reactions, such as β-hydride elimination with palladium catalysis or the reluctance of alkyl halides to undergo oxidative addition. To address this issue, nickel-catalysed cross-coupling processes can be used to form sp3–sp3 bonds that utilize organometallic nucleophiles and alkyl electrophiles. In particular, the coupling of alkyl halides with pre-generated organozinc, Grignard and organoborane species has been used to furnish diverse molecular structures. However, the manipulations required to produce these activated structures is inefficient, leading to poor step- and atom-economies. Moreover, the operational difficulties associated with making and using these reactive coupling partners, and preserving them through a synthetic sequence, has hindered their widespread adoption. A generically useful sp3–sp3 coupling technology that uses bench-stable, native organic functional groups, without the need for pre-functionalization or substrate derivatization, would therefore be valuable. Here we demonstrate that the synergistic merger of photoredox and nickel catalysis enables the direct formation of sp3–sp3 bonds using only simple carboxylic acids and alkyl halides as the nucleophilic and electrophilic coupling partners, respectively. This metallaphotoredox protocol is

  20. EDITORIAL: Catalysing progress Catalysing progress

    NASA Astrophysics Data System (ADS)

    Demming, Anna

    2010-01-01

    Examples of the merits of blue-sky research in the history of science are legion. The invention of the laser, celebrating its 50th anniversary this year, is an excellent example. When it was invented it was considered to be 'a solution waiting for a problem', and yet the level to which it has now infiltrated our day-to-day technological landscape speaks volumes. At the same time it is also true to say that the direction of research is also at times rightly influenced by the needs and concerns of the general public. Over recent years, growing concerns about the environment have had a noticeable effect on research in nanotechnology, motivating work on a range of topics from green nanomaterial synthesis [1] to high-efficiency solar cells [2] and hydrogen storage [3]. The impact of the world's energy consumption on the welfare of the planet is now an enduring and well founded concern. In the face of an instinctive reluctance to curtail habits of comfort and convenience and the appendages of culture and consumerism, research into renewable and more efficient energy sources seem an encouraging approach to alleviating an impending energy crisis. Fuel cells present one alternative to traditional combustion cells that have huge benefits in terms of the efficiency of energy conversion and the limited harmful emissions. In last week's issue of Nanotechnology, Chuan-Jian Zhong and colleagues at the State University of New York at Binghamton in the USA presented an overview of research on nanostructured catalysts in fuel cells [4]. The topical review includes insights into the interactions between nanoparticles and between nanoparticles and their substrate as well as control over the composition and nanostructure of catalysts. The review also serves to highlight how the flourishing of nanotechnology research has heralded great progress in the exploitation of catalysts with nanostructures ingeniously controlled to maximize surface area and optimize energetics for synthesis procedures. One man who was well aware of the role of nanostructured catalysts in the progress of material science research was the late Ulrich Gösele, director at the Max-Planck-Institut für Mikrostrukturphysik Halle, who passed away at the age of 60 on 8 November, 2009. Ulrich Gösele published over 750 papers of premium calibre research that have collectively been cited over 20,000 times. His research output includes a cornucopia of excellent work published in Nanotechnology, amongst which are a number of papers detailing the deft manipulation of nanocatalysts to control the quality and structure of nanomaterials [5-8]. Ulrich Gösele was a pioneer in nanoscience. In 1991, when the nanotechnology revolution was little more than a portentous rumble, he published a seminal report examining the effect of quantum confinement on the optical properties of silicon nanowires [9]. While we lament the loss to the community, we have much to celebrate in the insights his legacy has provided for the progress of materials science. It would be unwise to assume that science will or can ultimately advance in such a way as to allow ample means to indulge an unrestrained appetite for consumerism and energy consumption. As with most things, a balanced approach, considering solutions to the problem from many angles, seems sensible. Nonetheless, a browse through the latest literature leaves much cause for optimism for the positive role science can play in improving and sustaining our lifestyle. References [1] Mukherjee P, Roy M, Mandal B P, Dey G K, Mukherjee P K, Ghatak J, Tyagi A K and Kale S P 2008 Nanotechnology 19 075103 [2] Greenham N C and Grätzel M 2008 Nanotechnology 19 420201 [3] Vajo J, Pinkerton F and Stetson N 2009 Nanotechnology 20 200201 [4] Zhong C-J, Luo J, Fang B, Wanjala B N, Njoki P N, Loukrakpam R and Yin J 2010 Nanotechnology 21 062001 [5] Sivakov V A, Scholz A, Syrowatka F, Falk F, Gösele U and Christiansen S H 2009 Nanotechnology 20 405607 [6] Liu L, Lee W, Huang Z, Scholz R and Gösele U 2008 Nanotechnology 19 335604 [7] Fan H J et al 2006 Nanotechnology 17 S231-9 [8] Stelzner Th et al 2006 Nanotechnology 17 2895-8 [9] Lehmann V and Gösele U 1991 Appl. Phys. Lett. 58 856-8

  1. EDITORIAL: Catalysing progress Catalysing progress

    NASA Astrophysics Data System (ADS)

    Demming, Anna

    2010-01-01

    Examples of the merits of blue-sky research in the history of science are legion. The invention of the laser, celebrating its 50th anniversary this year, is an excellent example. When it was invented it was considered to be 'a solution waiting for a problem', and yet the level to which it has now infiltrated our day-to-day technological landscape speaks volumes. At the same time it is also true to say that the direction of research is also at times rightly influenced by the needs and concerns of the general public. Over recent years, growing concerns about the environment have had a noticeable effect on research in nanotechnology, motivating work on a range of topics from green nanomaterial synthesis [1] to high-efficiency solar cells [2] and hydrogen storage [3]. The impact of the world's energy consumption on the welfare of the planet is now an enduring and well founded concern. In the face of an instinctive reluctance to curtail habits of comfort and convenience and the appendages of culture and consumerism, research into renewable and more efficient energy sources seem an encouraging approach to alleviating an impending energy crisis. Fuel cells present one alternative to traditional combustion cells that have huge benefits in terms of the efficiency of energy conversion and the limited harmful emissions. In last week's issue of Nanotechnology, Chuan-Jian Zhong and colleagues at the State University of New York at Binghamton in the USA presented an overview of research on nanostructured catalysts in fuel cells [4]. The topical review includes insights into the interactions between nanoparticles and between nanoparticles and their substrate as well as control over the composition and nanostructure of catalysts. The review also serves to highlight how the flourishing of nanotechnology research has heralded great progress in the exploitation of catalysts with nanostructures ingeniously controlled to maximize surface area and optimize energetics for synthesis procedures. One man who was well aware of the role of nanostructured catalysts in the progress of material science research was the late Ulrich Gösele, director at the Max-Planck-Institut für Mikrostrukturphysik Halle, who passed away at the age of 60 on 8 November, 2009. Ulrich Gösele published over 750 papers of premium calibre research that have collectively been cited over 20,000 times. His research output includes a cornucopia of excellent work published in Nanotechnology, amongst which are a number of papers detailing the deft manipulation of nanocatalysts to control the quality and structure of nanomaterials [5-8]. Ulrich Gösele was a pioneer in nanoscience. In 1991, when the nanotechnology revolution was little more than a portentous rumble, he published a seminal report examining the effect of quantum confinement on the optical properties of silicon nanowires [9]. While we lament the loss to the community, we have much to celebrate in the insights his legacy has provided for the progress of materials science. It would be unwise to assume that science will or can ultimately advance in such a way as to allow ample means to indulge an unrestrained appetite for consumerism and energy consumption. As with most things, a balanced approach, considering solutions to the problem from many angles, seems sensible. Nonetheless, a browse through the latest literature leaves much cause for optimism for the positive role science can play in improving and sustaining our lifestyle. References [1] Mukherjee P, Roy M, Mandal B P, Dey G K, Mukherjee P K, Ghatak J, Tyagi A K and Kale S P 2008 Nanotechnology 19 075103 [2] Greenham N C and Grätzel M 2008 Nanotechnology 19 420201 [3] Vajo J, Pinkerton F and Stetson N 2009 Nanotechnology 20 200201 [4] Zhong C-J, Luo J, Fang B, Wanjala B N, Njoki P N, Loukrakpam R and Yin J 2010 Nanotechnology 21 062001 [5] Sivakov V A, Scholz A, Syrowatka F, Falk F, Gösele U and Christiansen S H 2009 Nanotechnology 20 405607 [6] Liu L, Lee W, Huang Z, Scholz R and Gösele U 2008 Nanotechnology 19 335604 [7] Fan H J et al 2006 Nanotechnology 1

  2. Graphic analysis of relaxation times of enzyme-catalysed reactions. An extension of the graphic method of King and Altman.

    PubMed Central

    Zhao, M

    1992-01-01

    An extension of the graphic method of King & Altman (1956) (J. Phys. Chem. 60, 1375-1378) is applied to the analysis of relaxation times of enzyme-catalysed reactions and a simple graphic method is presented. Clear-cut graphs, simple drawing, easy operation (without the need to perform the usual complex mathematical operations), and reliable results are the main characteristics of this kind of graphic method. A system of enzyme-catalysed reactions (E <--> ES <--> EP) is used as the actual example for illustrating the graphic method. PMID:1445198

  3. Direct conjugate alkylation of α,β-unsaturated carbonyls by Ti(III)-catalysed reductive umpolung of simple activated alkenes.

    PubMed

    Bichovski, Plamen; Haas, Thomas M; Keller, Manfred; Streuff, Jan

    2016-06-15

    The titanium(iii)-catalysed cross-selective reductive umpolung of Michael-acceptors represents a unique direct conjugate β-alkylation reaction. It allows the cross-selective preparation of 1,6- and 1,4-difunctionalised building blocks without the requirement of stoichiometric organometallic reagents. In this full paper, the development and scope of the titanium(iii)-catalysed cross-selective reductive umpolung of Michael-acceptors is described. Based on the observed selectivities and additional mechanistic experiments a refined mechanistic proposal is presented. PMID:26806535

  4. Eliminate Sweetened Drinks, Cut Kids' Sugar Intake

    MedlinePlus

    ... fullstory_161163.html Eliminate Sweetened Drinks, Cut Kids' Sugar Intake Average U.S. child consumes about 80 grams ... Looking for the quickest way to cut added sugar from your kid's diet? Eliminate sugar-sweetened drinks, ...

  5. Elimination communication as colic therapy.

    PubMed

    Jordan, Geraldine J

    2014-09-01

    Colic is generally defined as excessive crying in early infancy and can have negative consequences on the infant as well as on the infant's family life. Excessive crying can result in escalating parental stress levels, abusive caregiver response, increased risk of shaken baby syndrome and parental postpartum depression. In addition to excessive crying, symptoms and descriptors of infant colic include inconsolable crying, screaming, legs drawn up against the abdomen, furrowing of eyebrows, distended abdomen, arched back, passing gas, post-feeding crying and difficulty defecating. There are few well-designed, reproducible, randomized, large-scale studies which demonstrate efficacy of any therapeutic method for colic. An unexplored etiology is that colic is functionally related to a decrease in stooling frequency. Gut distention may periodically result in intensifying discomfort for the infant and in concomitant inconsolable crying. Elimination communication (EC; also known as Natural Infant Hygiene and sometimes referred to as infant potty training, baby-led potty training or assisted infant toilet training) involves the use of cues by which the infant signals to the caregiver that the infant needs to micturate or defecate. Such cues can include types of crying, squirming, straining, wriggling, grimacing, fussing, vocalizing, intent look at caregiver, red face, passing gas and grunting, many of which are the same initial symptoms related to the onset of colicky infant states. A caregiver's attentive and nurturant response to an infant's cues involve uncovering the infant's intergluteal cleft and cradling the infant gently and non-coercively in a supported, secure squatting position. This position will increase the infant's anorectal angle thus facilitating complete defecation. It is hypothesized that effective and timely elimination will cause increased physical comfort for the infant; colic symptoms will concomitantly decrease.

  6. Cosmic Ray elimination using the Wavelet Transform

    NASA Astrophysics Data System (ADS)

    Orozco-Aguilera, M. T.; Cruz, J.; Altamirano, L.; Serrano, A.

    2009-11-01

    In this work, we present a method for the automatic cosmic ray elimination in a single CCD exposure using the Wavelet Transform. The proposed method can eliminate cosmic rays of any shape or size. With this method we can eliminate over 95% of cosmic rays in a spectral image.

  7. Comparative cactus architecture and par interception

    SciTech Connect

    Geller, G.N.; Nobel, P.S. )

    1987-07-01

    Because CO{sup 2} uptake by cacti can be limited by low levels of photosynthetically active radiation (PAR) and because plant form affects PAR interception, various cactus forms were studied using a computer model, field measurements, and laboratory phototropic studies. Model predictions indicated that CO{sub 2} uptake by individual stems at an equinox was greatest when the stem were vertical, but at the summer and the winter solstice CO{sub 2} uptake was greatest for stems titled 30{degree} away from the equator. Stem tilting depended on form and taxonomic group. Not only can the shape of cacti be affected by PAR, but also shape influences PAR interception and hence CO{sub 2} uptake.

  8. Clinical inhibition of CYP2D6-catalysed metabolism by the antianginal agent perhexiline

    PubMed Central

    Davies, Benjamin J L; Coller, Janet K; James, Heather M; Gillis, David; Somogyi, Andrew A; Horowitz, John D; Morris, Raymond G; Sallustio, Benedetta C

    2004-01-01

    Aims Perhexiline is an antianginal agent that displays both saturable and polymorphic metabolism via CYP2D6. The aim of this study was to determine whether perhexiline produces clinically significant inhibition of CYP2D6-catalysed metabolism in angina patients. Methods The effects of perhexiline on CYP2D6-catalysed metabolism were investigated by comparing urinary total dextrorphan/dextromethorphan metabolic ratios following a single dose of dextromethorphan (16.4 mg) in eight matched control patients not taking perhexiline and 24 patients taking perhexiline. All of the patients taking perhexiline had blood drawn for CYP2D6 genotyping as well as to measure plasma perhexiline and cis-OH-perhexiline concentrations. Results Median (range) dextrorphan/dextromethorphan metabolic ratios were significantly higher (P < 0.0001) in control patients, 271.1 (40.3–686.1), compared with perhexiline-treated patients, 5.0 (0.3–107.9). In the perhexiline-treated group 10/24 patients had metabolic ratios consistent with poor metabolizer phenotypes; however, none was a genotypic poor metabolizer. Interestingly, 89% of patients who had phenocopied to poor metabolizers had only one functional CYP2D6 gene. There was a significant negative linear correlation between the log of the dextrorphan/dextromethorphan metabolic ratio and plasma perhexiline concentrations (r2 = 0.69, P < 0.0001). Compared with patients with at least two functional CYP2D6 genes, those with one functional gene were on similar perhexiline dosage regimens but had significantly higher plasma perhexiline concentrations, 0.73 (0.21–1.00) vs. 0.36 (0.04–0.69) mg l−1 (P = 0.04), lower cis-OH-perhexiline/perhexiline ratios, 2.85 (0.35–6.10) vs. 6.51 (1.84–11.67) (P = 0.03), and lower dextrorphan/dextromethorphan metabolic ratios, 2.51 (0.33–39.56) vs. 11.80 (2.90–36.93) (P = 0.005). Conclusions Perhexiline significantly inhibits CYP2D6-catalysed metabolism in angina patients. The plasma cis

  9. Proteinase-activated receptor-1 (PAR(1)) and PAR(2) but not PAR(4) mediate contraction in human and guinea-pig gallbladders.

    PubMed

    Lee, M-C; Huang, S-C

    2008-04-01

    Proteinase-activated receptor-1 (PAR(1)) and PAR(2) mediate contraction in the guinea-pig gallbladder. To investigate and compare the effects mediated by PARs in the human gallbladder with those in the guinea-pig gallbladder, we measured contractions of isolated human and guinea-pig gallbladder strips caused by PAR agonists. Results in human were similar to those in guinea-pig gallbladder. The PAR(1) agonists, thrombin, TFLLR-NH2 and SFLLRN-NH2, as well as the PAR(2) agonists, trypsin, SLIGKV-NH2 and SLIGRL-NH2, caused contraction in both human and guinea-pig gallbladders. These indicate the existence of PAR(1) and PAR(2) mediating gallbladder contraction. Furthermore, the existence of PAR(1) and PAR(2) in the human gallbladder was confirmed by reverse transcription-polymerase chain reaction. In contrast, FSLLR-NH2, a PAR(1) control peptide, and VKGILS-NH2, a PAR(2) control peptide, as well as three PAR(4) agonists, GYPGKF-NH2, GYPGQV-NH2 and AYPGKF-NH2, did not cause any contraction or relaxation. The contractile responses to TFLLR-NH2, SFLLRN-NH2 and trypsin in both human and guinea-pig gallbladders were insensitive to atropine and tetrodotoxin, suggesting direct effects. These results demonstrate that, similar to the guinea-pig gallbladder, both PAR(1) and PAR(2) but not PAR(4) mediate muscle contraction in the human gallbladder. PAR(1) and PAR(2) may play important roles in the control of both human and guinea-pig gallbladder motility. PMID:18179608

  10. Proteinase-activated receptor-1 (PAR1) and PAR2 mediate relaxation of guinea pig internal anal sphincter.

    PubMed

    Huang, Shih-Che

    2014-02-10

    Activation of proteinase-activated receptor-1 (PAR1) and PAR2 stimulates contraction of the rat but relaxation of the guinea pig colon. The aim of the present study was to investigate PAR effects on internal anal sphincter (IAS) motility. We measured relaxation of isolated muscle strips from the guinea pig IAS caused by PAR agonists using isometric transducers. Reverse transcription polymerase chain reaction (RT-PCR) was performed to determine the existence of PAR. In the IAS, thrombin and PAR1 peptide agonists TFLLR-NH2 and SFLLRN-NH2 evoked moderate to marked relaxation in a concentration-dependent manner. In addition, trypsin and PAR2 peptide agonists 2-furoyl-LIGRLO-NH2, SLIGRL-NH2 and SLIGKV-NH2 produced relaxation. In contrast, both PAR1 and PAR2 inactive control peptides did not elicit relaxation. Furthermore, the selective PAR1 antagonist vorapaxar and PAR2 antagonist GB 83 specifically inhibited thrombin and trypsin-induced relaxations, respectively. RT-PCR revealed the presence of PAR1 and PAR2 in the IAS. This indicates that PAR1 and PAR2 mediate the IAS relaxation. The relaxant responses of TFLLR-NH2 and trypsin were attenuated by N(omega)-Nitro-L-arginine (L-NNA), indicating involvement of NO. These responses were not affected by tetrodotoxin, implying that the PAR effects are not neurally mediated. On the other hand, PAR4 agonists GYPGKF-NH2, GYPGQV-NH2 and AYPGKF-NH2 did not cause relaxation or contraction, suggesting that PAR4 is not involved in the sphincter motility. Taken together, these results demonstrate that both PAR1 and PAR2 mediate relaxation of the guinea pig IAS through the NO pathway. PAR1 and PAR2 may regulate IAS tone and might be potential therapeutic targets for anal motility disorders. PMID:24631471

  11. Costs and financial feasibility of malaria elimination

    PubMed Central

    Sabot, Oliver; Cohen, Justin M; Hsiang, Michelle S; Kahn, James G; Basu, Suprotik; Tang, Linhua; Zheng, Bin; Gao, Qi; Zou, Linda; Tatarsky, Allison; Aboobakar, Shahina; Usas, Jennifer; Barrett, Scott; Cohen, Jessica L; Jamison, Dean T; Feachem, Richard GA

    2010-01-01

    Summary The marginal costs and benefits of converting malaria programmes from a control to an elimination goal are central to strategic decisions, but empirical evidence is scarce. We present a conceptual framework to assess the economics of elimination and analyse a central component of that framework—potential short-term to medium-term financial savings. After a review that showed a dearth of existing evidence, the net present value of elimination in five sites was calculated and compared with effective control. The probability that elimination would be cost-saving over 50 years ranged from 0% to 42%, with only one site achieving cost-savings in the base case. These findings show that financial savings should not be a primary rationale for elimination, but that elimination might still be a worthy investment if total benefits are sufficient to outweigh marginal costs. Robust research into these elimination benefits is urgently needed. PMID:21035839

  12. A palladium-catalysed multicomponent coupling approach to conjugated poly(1,3-dipoles) and polyheterocycles

    PubMed Central

    Leitch, David C.; Kayser, Laure V.; Han, Zhi-Yong; Siamaki, Ali R.; Keyzer, Evan N.; Gefen, Ashley; Arndtsen, Bruce A.

    2015-01-01

    Conjugated polymers have emerged over the past several decades as key components for a range of applications, including semiconductors, molecular wires, sensors, light switchable transistors and OLEDs. Nevertheless, the construction of many such polymers, especially highly substituted variants, typically involves a multistep synthesis. This can limit the ability to both access and tune polymer structures for desired properties. Here we show an alternative approach to synthesize conjugated materials: a metal-catalysed multicomponent polymerization. This reaction assembles multiple monomer units into a new polymer containing reactive 1,3-dipoles, which can be modified using cycloaddition reactions. In addition to the synthetic ease of this approach, its modularity allows easy adaptation to incorporate a range of desired substituents, all via one-pot reactions. PMID:26077769

  13. Base catalysed isomerisation of aldoses of the arabino and lyxo series in the presence of aluminate.

    PubMed

    Ekeberg, Dag; Morgenlie, Svein; Stenstrøm, Yngve

    2002-04-30

    Base-catalysed isomerisation of aldoses of the arabino and lyxo series in aluminate solution has been investigated. L-Arabinose and D-galactose give L-erythro-2-pentulose (L-ribulose) and D-lyxo-2-hexulose (D-tagatose), respectively, in good yields, whereas lower reactivity is observed for 6-deoxy-D-galactose (D-fucose). From D-lyxose, D-mannose and 6-deoxy-L-mannose (L-rhamnose) are obtained mixtures of ketoses and C-2 epimeric aldoses. Small amounts of the 3-epimers of the ketoses were also formed. 6-Deoxy-L-arabino-2-hexulose (6-deoxy-L-fructose) and 6-deoxy-L-glucose (L-quinovose) were formed in low yields from 6-deoxy-L-mannose and isolated as their O-isopropylidene derivatives. Explanations of the differences in reactivity and course of the reaction have been suggested on the basis of steric effects.

  14. RNA with iron(II) as a cofactor catalyses electron transfer

    NASA Astrophysics Data System (ADS)

    Hsiao, Chiaolong; Chou, I.-Chun; Okafor, C. Denise; Bowman, Jessica C.; O'Neill, Eric B.; Athavale, Shreyas S.; Petrov, Anton S.; Hud, Nicholas V.; Wartell, Roger M.; Harvey, Stephen C.; Williams, Loren Dean

    2013-06-01

    Mg2+ is essential for RNA folding and catalysis. However, for the first 1.5 billion years of life on Earth RNA inhabited an anoxic Earth with abundant and benign Fe2+. We hypothesize that Fe2+ was an RNA cofactor when iron was abundant, and was substantially replaced by Mg2+ during a period known as the ‘great oxidation’, brought on by photosynthesis. Here, we demonstrate that reversing this putative metal substitution in an anoxic environment, by removing Mg2+ and replacing it with Fe2+, expands the catalytic repertoire of RNA. Fe2+ can confer on some RNAs a previously uncharacterized ability to catalyse single-electron transfer. We propose that RNA function, in analogy with protein function, can be understood fully only in the context of association with a range of possible metals. The catalysis of electron transfer, requisite for metabolic activity, may have been attenuated in RNA by photosynthesis and the rise of O2.

  15. Acceptorless Dehydrogenative Oxidation of Secondary Alcohols Catalysed by Cp*Ir(III) -NHC Complexes.

    PubMed

    Gülcemal, Süleyman; Gülcemal, Derya; Whitehead, George F S; Xiao, Jianliang

    2016-07-18

    A series of new Ir(III) complexes with carbene ligands that contain a range of benzyl wingtip groups have been prepared and fully characterised by NMR spectroscopy, HRMS, elemental analysis and X-ray diffraction. All the complexes were active in the acceptorless dehydrogenation of alcohol substrates in 2,2,2-trifluoroethanol to give the corresponding carbonyl compounds. The most active complex bore an electron-rich carbene ligand; this complex was used to catalyse the highly efficient and chemoselective dehydrogenation of a wide range of secondary alcohols to their respective ketones, with turnover numbers up to 1660. Mechanistic studies suggested that the turnover of the dehydrogenation reaction is limited by the H2 -formation step. PMID:27321021

  16. Efficient and selective N-alkylation of amines with alcohols catalysed by manganese pincer complexes

    PubMed Central

    Elangovan, Saravanakumar; Neumann, Jacob; Sortais, Jean-Baptiste; Junge, Kathrin; Darcel, Christophe; Beller, Matthias

    2016-01-01

    Borrowing hydrogen (or hydrogen autotransfer) reactions represent straightforward and sustainable C–N bond-forming processes. In general, precious metal-based catalysts are employed for this effective transformation. In recent years, the use of earth abundant and cheap non-noble metal catalysts for this process attracted considerable attention in the scientific community. Here we show that the selective N-alkylation of amines with alcohols can be catalysed by defined PNP manganese pincer complexes. A variety of substituted anilines are monoalkylated with different (hetero)aromatic and aliphatic alcohols even in the presence of other sensitive reducible functional groups. As a special highlight, we report the chemoselective monomethylation of primary amines using methanol under mild conditions. PMID:27708259

  17. Palladium-catalysed formation of vicinal all-carbon quaternary centres via propargylation

    PubMed Central

    Huang, Xin; Wu, Shangze; Wu, Wangteng; Li, Pengbin; Fu, Chunling; Ma, Shengming

    2016-01-01

    Construction of two vicinal all-carbon quaternary carbon centres is of great importance due to the common presence of such units in natural and unnatural molecules with attractive functions. However, it remains a significant challenge. Here, we have developed a palladium-catalysed general coupling for the efficient connection of two tertiary carbon atoms: Specifically, propargylic carbonate has been treated with a fully loaded soft functionalized nucleophile to connect such two fully loaded carbon atoms with a simple palladium catalyst. It is observed that the central chirality in the optically active tertiary propargylic carbonates has been remembered and transferred into the products with very high efficiency. The triple bond and the functional groups such as ester, cyano and unsaturated C–C bonds make this method a relatively general solution for such a purpose due to their high synthetic versatility. PMID:27558203

  18. Chlorophyll catalyse the photo-transformation of carcinogenic benzo[a]pyrene in water

    NASA Astrophysics Data System (ADS)

    Luo, Lijuan; Lai, Xueying; Chen, Baowei; Lin, Li; Fang, Ling; Tam, Nora F. Y.; Luan, Tiangang

    2015-08-01

    Algal blooms cause great damage to water quality and aquaculture. However, this study showed that dead algal cells and chlorophyll could accelerate the photo-transformation of benzo[a]pyrene (BaP), a ubiquitous and persistent pollutant with potently mutagenic and carcinogenic toxicities, under visible light irradiation. Chlorophyll was found to be the major active substance in dead algal cells, and generated a high level of singlet oxygen to catalyse the photo-transformation of BaP. According to various BaP metabolites formed, the degradation mechanism was proposed as that chlorophyll in dead algal cells photo-oxidized BaP to quinones via photocatalytic generation of singlet oxygen. The results provided a good insight into the role of chlorophyll in the photo-transformation of organic contaminants and could be a possible remediation strategy of organic pollutants in natural environment.

  19. Palladium-catalysed formation of vicinal all-carbon quaternary centres via propargylation

    NASA Astrophysics Data System (ADS)

    Huang, Xin; Wu, Shangze; Wu, Wangteng; Li, Pengbin; Fu, Chunling; Ma, Shengming

    2016-08-01

    Construction of two vicinal all-carbon quaternary carbon centres is of great importance due to the common presence of such units in natural and unnatural molecules with attractive functions. However, it remains a significant challenge. Here, we have developed a palladium-catalysed general coupling for the efficient connection of two tertiary carbon atoms: Specifically, propargylic carbonate has been treated with a fully loaded soft functionalized nucleophile to connect such two fully loaded carbon atoms with a simple palladium catalyst. It is observed that the central chirality in the optically active tertiary propargylic carbonates has been remembered and transferred into the products with very high efficiency. The triple bond and the functional groups such as ester, cyano and unsaturated C-C bonds make this method a relatively general solution for such a purpose due to their high synthetic versatility.

  20. Enantioselective construction of quaternary N-heterocycles by palladium-catalysed decarboxylative allylic alkylation of lactams

    NASA Astrophysics Data System (ADS)

    Behenna, Douglas C.; Liu, Yiyang; Yurino, Taiga; Kim, Jimin; White, David E.; Virgil, Scott C.; Stoltz, Brian M.

    2012-02-01

    The enantioselective synthesis of nitrogen-containing heterocycles (N-heterocycles) represents a substantial chemical research effort and resonates across numerous disciplines, including the total synthesis of natural products and medicinal chemistry. In this Article, we describe the highly enantioselective palladium-catalysed decarboxylative allylic alkylation of readily available lactams to form 3,3-disubstituted pyrrolidinones, piperidinones, caprolactams and structurally related lactams. Given the prevalence of quaternary N-heterocycles in biologically active alkaloids and pharmaceutical agents, we envisage that our method will provide a synthetic entry into the de novo asymmetric synthesis of such structures. As an entry for these investigations we demonstrate how the described catalysis affords enantiopure quaternary lactams that intercept synthetic intermediates previously used in the synthesis of the Aspidosperma alkaloids quebrachamine and rhazinilam, but that were previously only available by chiral auxiliary approaches or as racemic mixtures.

  1. Regio- and stereodivergent antibiotic oxidative carbocyclizations catalysed by Rieske oxygenase-like enzymes

    NASA Astrophysics Data System (ADS)

    Sydor, Paulina K.; Barry, Sarah M.; Odulate, Olanipekun M.; Barona-Gomez, Francisco; Haynes, Stuart W.; Corre, Christophe; Song, Lijiang; Challis, Gregory L.

    2011-05-01

    Oxidative cyclizations, exemplified by the biosynthetic assembly of the penicillin nucleus from a tripeptide precursor, are arguably the most synthetically powerful implementation of C-H activation reactions in nature. Here, we show that Rieske oxygenase-like enzymes mediate regio- and stereodivergent oxidative cyclizations to form 10- and 12-membered carbocyclic rings in the key steps of the biosynthesis of the antibiotics streptorubin B and metacycloprodigiosin, respectively. These reactions represent the first examples of oxidative carbocyclizations catalysed by non-haem iron-dependent oxidases and define a novel type of catalytic activity for Rieske enzymes. A better understanding of how these enzymes achieve such remarkable regio- and stereocontrol in the functionalization of unactivated hydrocarbon chains will greatly facilitate the development of selective man-made C-H activation catalysts.

  2. Acidic resin-catalysed conversion of fructose into furan derivatives in low boiling point solvents.

    PubMed

    Zhu, Hong; Cao, Quan; Li, Chunhu; Mu, Xindong

    2011-09-27

    Conversion of fructose into furan derivatives 5-hydroxymethylfurfural (HMF) and 5-methoxymethylfurfural (MMF) is performed in tetrahydrofuran (THF) and methanol-organic solvent systems, catalysed by an acidic resin Amberlyst-15. The melted fructose can be converted into HMF on the surface of the solid resin catalyst in the presence of THF as an extracting phase, which is a good solvent for HMF and other by-products. The solid resin catalyst can be reused eleven times without losing its catalytic ability, with an average HMF yield of approximately 50%. Upon the addition of methanol, the generated HMF can further react with methanol to form MMF, and the total yield of HMF and MMF could be promoted to 65%. GC-MS analysis confirms the formation of a small amount of methyl levulinate in methanolorganic solvent system.

  3. Chlorophyll catalyse the photo-transformation of carcinogenic benzo[a]pyrene in water

    PubMed Central

    Luo, Lijuan; Lai, Xueying; Chen, Baowei; Lin, Li; Fang, Ling; Tam, Nora F. Y.; Luan, Tiangang

    2015-01-01

    Algal blooms cause great damage to water quality and aquaculture. However, this study showed that dead algal cells and chlorophyll could accelerate the photo-transformation of benzo[a]pyrene (BaP), a ubiquitous and persistent pollutant with potently mutagenic and carcinogenic toxicities, under visible light irradiation. Chlorophyll was found to be the major active substance in dead algal cells, and generated a high level of singlet oxygen to catalyse the photo-transformation of BaP. According to various BaP metabolites formed, the degradation mechanism was proposed as that chlorophyll in dead algal cells photo-oxidized BaP to quinones via photocatalytic generation of singlet oxygen. The results provided a good insight into the role of chlorophyll in the photo-transformation of organic contaminants and could be a possible remediation strategy of organic pollutants in natural environment. PMID:26239357

  4. On the Mechanism of the Digold(I)-Hydroxide-Catalysed Hydrophenoxylation of Alkynes.

    PubMed

    Gómez-Suárez, Adrián; Oonishi, Yoshihiro; Martin, Anthony R; Vummaleti, Sai V C; Nelson, David J; Cordes, David B; Slawin, Alexandra M Z; Cavallo, Luigi; Nolan, Steven P; Poater, Albert

    2016-01-18

    Herein, we present a detailed investigation of the mechanistic aspects of the dual gold-catalysed hydrophenoxylation of alkynes by both experimental and computational methods. The dissociation of [{Au(NHC)}2 (μ-OH)][BF4 ] is essential to enter the catalytic cycle, and this step is favoured by the presence of bulky, non-coordinating counter ions. Moreover, in silico studies confirmed that phenol does not only act as a reactant, but also as a co-catalyst, lowering the energy barriers of several transition states. A gem-diaurated species might form during the reaction, but this lies deep within a potential energy well, and is likely to be an "off-cycle" rather than an "in-cycle" intermediate. PMID:26662656

  5. Bray-Liebhafsky and non-catalysed Briggs-Rauscher oscillating reactions

    NASA Astrophysics Data System (ADS)

    Schmitz, Guy; Furrow, Stanley D.

    2016-02-01

    In order to propose mechanisms of complicated chemical systems, it is necessary to study simpler subsystems. The mechanism we have proposed for the Bray-Liebhafsky (BL) oscillating reaction is based on kinetic studies of several reactions of iodine compounds between them and with hydrogen peroxide. Because the reactants of the non-catalysed Briggs-Rauscher (BR) oscillating reaction are the same as those of the BL reaction plus malonic acid, we propose now to extend the mechanism of the BL reaction to the BR reaction. With this aim, we add radical reactions of iodine compounds and of malonic acid. The choice of these reactions is based on our recent study of the unusual kinetics of the iodate reduction by high concentrations of hydrogen peroxide.

  6. Chlorophyll catalyse the photo-transformation of carcinogenic benzo[a]pyrene in water.

    PubMed

    Luo, Lijuan; Lai, Xueying; Chen, Baowei; Lin, Li; Fang, Ling; Tam, Nora F Y; Luan, Tiangang

    2015-08-04

    Algal blooms cause great damage to water quality and aquaculture. However, this study showed that dead algal cells and chlorophyll could accelerate the photo-transformation of benzo[a]pyrene (BaP), a ubiquitous and persistent pollutant with potently mutagenic and carcinogenic toxicities, under visible light irradiation. Chlorophyll was found to be the major active substance in dead algal cells, and generated a high level of singlet oxygen to catalyse the photo-transformation of BaP. According to various BaP metabolites formed, the degradation mechanism was proposed as that chlorophyll in dead algal cells photo-oxidized BaP to quinones via photocatalytic generation of singlet oxygen. The results provided a good insight into the role of chlorophyll in the photo-transformation of organic contaminants and could be a possible remediation strategy of organic pollutants in natural environment.

  7. Efficient and selective N-alkylation of amines with alcohols catalysed by manganese pincer complexes

    NASA Astrophysics Data System (ADS)

    Elangovan, Saravanakumar; Neumann, Jacob; Sortais, Jean-Baptiste; Junge, Kathrin; Darcel, Christophe; Beller, Matthias

    2016-10-01

    Borrowing hydrogen (or hydrogen autotransfer) reactions represent straightforward and sustainable C-N bond-forming processes. In general, precious metal-based catalysts are employed for this effective transformation. In recent years, the use of earth abundant and cheap non-noble metal catalysts for this process attracted considerable attention in the scientific community. Here we show that the selective N-alkylation of amines with alcohols can be catalysed by defined PNP manganese pincer complexes. A variety of substituted anilines are monoalkylated with different (hetero)aromatic and aliphatic alcohols even in the presence of other sensitive reducible functional groups. As a special highlight, we report the chemoselective monomethylation of primary amines using methanol under mild conditions.

  8. Chlorophyll catalyse the photo-transformation of carcinogenic benzo[a]pyrene in water.

    PubMed

    Luo, Lijuan; Lai, Xueying; Chen, Baowei; Lin, Li; Fang, Ling; Tam, Nora F Y; Luan, Tiangang

    2015-01-01

    Algal blooms cause great damage to water quality and aquaculture. However, this study showed that dead algal cells and chlorophyll could accelerate the photo-transformation of benzo[a]pyrene (BaP), a ubiquitous and persistent pollutant with potently mutagenic and carcinogenic toxicities, under visible light irradiation. Chlorophyll was found to be the major active substance in dead algal cells, and generated a high level of singlet oxygen to catalyse the photo-transformation of BaP. According to various BaP metabolites formed, the degradation mechanism was proposed as that chlorophyll in dead algal cells photo-oxidized BaP to quinones via photocatalytic generation of singlet oxygen. The results provided a good insight into the role of chlorophyll in the photo-transformation of organic contaminants and could be a possible remediation strategy of organic pollutants in natural environment. PMID:26239357

  9. Influence of Fe(2+)-catalysed iron oxide recrystallization on metal cycling.

    PubMed

    Latta, Drew E; Gorski, Christopher A; Scherer, Michelle M

    2012-12-01

    Recent work has indicated that iron (oxyhydr-)oxides are capable of structurally incorporating and releasing metals and nutrients as a result of Fe2+-induced iron oxide recrystallization. In the present paper, we briefly review the current literature examining the mechanisms by which iron oxides recrystallize and summarize how recrystallization affects metal incorporation and release. We also provide new experimental evidence for the Fe2+-induced release of structural manganese from manganese-doped goethite. Currently, the exact mechanism(s) for Fe2+-induced recrystallization remain elusive, although they are likely to be both oxide-and metal-dependent. We conclude by discussing some future research directions for Fe2+-catalysed iron oxide recrystallization.

  10. Acceptorless Dehydrogenative Oxidation of Secondary Alcohols Catalysed by Cp*Ir(III) -NHC Complexes.

    PubMed

    Gülcemal, Süleyman; Gülcemal, Derya; Whitehead, George F S; Xiao, Jianliang

    2016-07-18

    A series of new Ir(III) complexes with carbene ligands that contain a range of benzyl wingtip groups have been prepared and fully characterised by NMR spectroscopy, HRMS, elemental analysis and X-ray diffraction. All the complexes were active in the acceptorless dehydrogenation of alcohol substrates in 2,2,2-trifluoroethanol to give the corresponding carbonyl compounds. The most active complex bore an electron-rich carbene ligand; this complex was used to catalyse the highly efficient and chemoselective dehydrogenation of a wide range of secondary alcohols to their respective ketones, with turnover numbers up to 1660. Mechanistic studies suggested that the turnover of the dehydrogenation reaction is limited by the H2 -formation step.

  11. Palladium-catalysed formation of vicinal all-carbon quaternary centres via propargylation.

    PubMed

    Huang, Xin; Wu, Shangze; Wu, Wangteng; Li, Pengbin; Fu, Chunling; Ma, Shengming

    2016-01-01

    Construction of two vicinal all-carbon quaternary carbon centres is of great importance due to the common presence of such units in natural and unnatural molecules with attractive functions. However, it remains a significant challenge. Here, we have developed a palladium-catalysed general coupling for the efficient connection of two tertiary carbon atoms: Specifically, propargylic carbonate has been treated with a fully loaded soft functionalized nucleophile to connect such two fully loaded carbon atoms with a simple palladium catalyst. It is observed that the central chirality in the optically active tertiary propargylic carbonates has been remembered and transferred into the products with very high efficiency. The triple bond and the functional groups such as ester, cyano and unsaturated C-C bonds make this method a relatively general solution for such a purpose due to their high synthetic versatility. PMID:27558203

  12. Transition metal-catalysed (4 + 3) cycloaddition reactions involving allyl cations.

    PubMed

    Fernández, Israel; Mascareñas, José Luis

    2012-01-28

    In this emerging area article, we focus on novel intramolecular transition metal catalysed (4 + 3)-cycloaddition reactions of allenedienes in which the allene acts as an allylic-cation surrogate. This process has emerged as a powerful tool for the construction not only of complex seven-membered rings containing compounds but also different types of useful molecular skeletons by the proper selection of the catalyst. The transformation proceeds with high chemo- and stereoselectivity mainly because it occurs through an exo-like concerted transition state which exhibits a clear in-plane aromatic character. Despite that, different reaction mechanisms (i.e. stepwise processes) are also possible depending on the nucleophilicity of the diene moiety.

  13. Copper catalysed azide-alkyne cycloaddition (CuAAC) in liquid ammonia.

    PubMed

    Ji, Pengju; Atherton, John H; Page, Michael I

    2012-10-21

    Copper(I) catalysed azide-alkyne cycloaddition reactions (CuAAC) occur smoothly in liquid ammonia (LNH(3)) at room temperature to give exclusively 1,4-substituted 1,2,3-triazoles with excellent yields (up to 99%). The CuAAC reactions in liquid ammonia require relatively small amounts of copper(I) catalyst (0.5 mole%) compared with that in conventional solvents. The product can be obtained conveniently by simply evaporation of ammonia, indicating its potential application in industry. The rate of the CuAAC reaction in liquid ammonia shows a second order dependence on the copper(I) concentration and the reaction occurs only with terminal alkynes. Deuterium exchange experiments with phenyl acetylene-d(1) show that the acidity of the alkyne is increased at least 1000-fold with catalytic amounts of copper(I) in liquid ammonia. The mechanism of the CuAAC reaction in liquid ammonia is discussed. PMID:22930181

  14. Scope and limitations of the dual-gold-catalysed hydrophenoxylation of alkynes

    PubMed Central

    Gómez-Suárez, Adrián; Oonishi, Yoshihiro; Martin, Anthony R

    2016-01-01

    Summary Due to the synthetic advantages presented by the dual-gold-catalysed hydrophenoxylation of alkynes, a thorough study of this reaction was carried out in order to fully define the scope and limitations of the methodology. The protocol tolerates a wide range of functional groups, such as nitriles, ketones, esters, aldehydes, ketals, naphthyls, allyls or polyphenols, in a milder and more efficient manner than the previously reported methodologies. We have also identified that while we are able to use highly steric hindered phenols, small changes on the steric bulk of the alkynes have a dramatic effect on the reactivity. More importantly, we have observed that the use of substrates that facilitate the formation of diaurated species such as gem-diaurated or σ,π-digold–acetylide species, hinder the catalytic activity. Moreover, we have identified that the use of directing groups in unsymmetrical alkynes can help to achieve high regioselectivity in the hydrophenoxylation. PMID:26977176

  15. Laccase catalysed grafting of phenolic onto xylan to improve its applicability in films

    NASA Astrophysics Data System (ADS)

    Pei, Jicheng; Wang, Bing; Zhang, Fangdong; Li, Zhongyang; Yin, Yunbei; Zhang, Dongxu

    2015-07-01

    Xylan can be tailored for various value-added applications. However, its use in aqueous systems is hampered by its complex structure, and small molecular weight. This research aimed at improving the xylan molecular weight and changing its structure. Laccase-catalysed oxidation of 4-coumaric acid (PCA), ferulic acid (FA), syringaldehyde (SD), and vanillin (VA) onto xylan was grafted to study the changes in its structure, tensile properties, and antibacterial activities. A Fourier transform infrared (FTIR) spectrum analyser was used to observe the changes in functional groups of xylan. The results showed a band at 1635 cm-1 corresponding to the stretching vibration of conjugated carbonyl carboxy hemoglobin and a benzene ring structure were strengthened; the appearance of a new band between 1200 cm-1 and 1270 cm-1 corresponding to alkyl ethers on the aryl C-O stretching vibration was due to the fact that during the grafting process, the number of benzene ring structures increased and covalent connections occurred between phenols and xylan. The reaction mechanism for the laccase-catalysed oxidation of phenol compounds onto xylan was preliminary explored by 13C-NMR. The results showed that PCA-xylan, FA-xylan graft poly onto xylan by Cγ ester bond, SD-xylan graft poly onto xylan by ether bond and an ester bond, and VD-xylan graft poly onto xylan by ether bond. The film strength of xylan derivatives has been significantly increased, especially for the PCA-xylan derivative. The increases in tensile stress at break, tensile strength, tensile yield stress, and Young's modulus were: 24.04%, 31.30%, 55.56%, and 28.21%, respectively. After laccase/phenolics were modified, xylan had a good antibacterial effect to E. coli, Corynebacterium glutamicum, and Bacillus subtilis. The SD-xylan, FA-xylan, and PCA-xylan showed a greater efficacy against E. coli, Corynebacterium glutamicum, and Bacillus subtilis, respectively.

  16. Techniques for measuring intercepted and absorbed PAR in corn canopies

    NASA Technical Reports Server (NTRS)

    Gallo, K. P.; Daughtry, C. S. T.

    1984-01-01

    The quantity of radiation potentially available for photosynthesis that is captured by the crop is best described as absorbed photosynthetically active radiation (PAR). Absorbed PAR (APAR) is the difference between descending and ascending fluxes. The four components of APAR were measured above and within two planting densities of corn (Zea mays L.) and several methods of measuring and estimating APAR were examined. A line quantum sensor that spatially averages the photosynthetic photon flux density provided a rapid and portable method of measuring APAR. PAR reflectance from the soil (Typic Argiaquoll) surface decreased from 10% to less than 1% of the incoming PAR as the canopy cover increased. PAR reflectance from the canopy decreased to less than 3% at maximum vegetative cover. Intercepted PAR (1 - transmitted PAR) generally overestimated absorbed PAR by less than 4% throughout most of the growing season. Thus intercepted PAR appears to be a reasonable estimate of absorbed PAR.

  17. Elimination of Onchocerciasis from Mexico

    PubMed Central

    Rodríguez-Pérez, Mario A.; Fernández-Santos, Nadia A.; Orozco-Algarra, María E.; Rodríguez-Atanacio, José A.; Domínguez-Vázquez, Alfredo; Rodríguez-Morales, Kristel B.; Real-Najarro, Olga; Prado-Velasco, Francisco G.; Cupp, Eddie W.; Richards, Frank O.; Hassan, Hassan K.; González-Roldán, Jesús F.; Kuri-Morales, Pablo A.; Unnasch, Thomas R.

    2015-01-01

    Background Mexico is one of the six countries formerly endemic for onchocerciasis in Latin America. Transmission has been interrupted in the three endemic foci of that country and mass drug distribution has ceased. Three years after mass drug distribution ended, post-treatment surveillance (PTS) surveys were undertaken which employed entomological indicators to check for transmission recrudescence. Methodology/Principal findings In-depth entomologic assessments were performed in 18 communities in the three endemic foci of Mexico. None of the 108,212 Simulium ochraceum s.l. collected from the three foci were found to contain parasite DNA when tested by polymerase chain reaction-enzyme-linked immunosorbent assay (PCR-ELISA), resulting in a maximum upper bound of the 95% confidence interval (95%-ULCI) of the infective rate in the vectors of 0.035/2,000 flies examined. This is an order of magnitude below the threshold of a 95%-ULCI of less than one infective fly per 2,000 flies tested, the current entomological criterion for interruption of transmission developed by the international community. The point estimate of seasonal transmission potential (STP) was zero, and the upper bound of the 95% confidence interval for the STP ranged from 1.2 to 1.7 L3/person/season in the different foci. This value is below all previous estimates for the minimum transmission potential required to maintain the parasite population. Conclusions/Significance The results from the in-depth entomological post treatment surveillance surveys strongly suggest that transmission has not resumed in the three foci of Mexico during the three years since the last distribution of ivermectin occurred; it was concluded that transmission remains undetectable without intervention, and Onchocerca volvulus has been eliminated from Mexico. PMID:26161558

  18. Mating ecology explains patterns of genome elimination

    PubMed Central

    Gardner, Andy; Ross, Laura

    2014-01-01

    Genome elimination – whereby an individual discards chromosomes inherited from one parent, and transmits only those inherited from the other parent – is found across thousands of animal species. It is more common in association with inbreeding, under male heterogamety, in males, and in the form of paternal genome elimination. However, the reasons for this broad pattern remain unclear. We develop a mathematical model to determine how degree of inbreeding, sex determination, genomic location, pattern of gene expression and parental origin of the eliminated genome interact to determine the fate of genome-elimination alleles. We find that: inbreeding promotes paternal genome elimination in the heterogametic sex; this may incur population extinction under female heterogamety, owing to eradication of males; and extinction is averted under male heterogamety, owing to countervailing sex-ratio selection. Thus, we explain the observed pattern of genome elimination. Our results highlight the interaction between mating system, sex-ratio selection and intragenomic conflict. PMID:25328085

  19. Mapping residual transmission for malaria elimination.

    PubMed

    Reiner, Robert C; Le Menach, Arnaud; Kunene, Simon; Ntshalintshali, Nyasatu; Hsiang, Michelle S; Perkins, T Alex; Greenhouse, Bryan; Tatem, Andrew J; Cohen, Justin M; Smith, David L

    2015-12-29

    Eliminating malaria from a defined region involves draining the endemic parasite reservoir and minimizing local malaria transmission around imported malaria infections . In the last phases of malaria elimination, as universal interventions reap diminishing marginal returns, national resources must become increasingly devoted to identifying where residual transmission is occurring. The needs for accurate measures of progress and practical advice about how to allocate scarce resources require new analytical methods to quantify fine-grained heterogeneity in malaria risk. Using routine national surveillance data from Swaziland (a sub-Saharan country on the verge of elimination), we estimated individual reproductive numbers. Fine-grained maps of reproductive numbers and local malaria importation rates were combined to show 'malariogenic potential', a first for malaria elimination. As countries approach elimination, these individual-based measures of transmission risk provide meaningful metrics for planning programmatic responses and prioritizing areas where interventions will contribute most to malaria elimination.

  20. Mating ecology explains patterns of genome elimination.

    PubMed

    Gardner, Andy; Ross, Laura

    2014-12-01

    Genome elimination - whereby an individual discards chromosomes inherited from one parent, and transmits only those inherited from the other parent - is found across thousands of animal species. It is more common in association with inbreeding, under male heterogamety, in males, and in the form of paternal genome elimination. However, the reasons for this broad pattern remain unclear. We develop a mathematical model to determine how degree of inbreeding, sex determination, genomic location, pattern of gene expression and parental origin of the eliminated genome interact to determine the fate of genome-elimination alleles. We find that: inbreeding promotes paternal genome elimination in the heterogametic sex; this may incur population extinction under female heterogamety, owing to eradication of males; and extinction is averted under male heterogamety, owing to countervailing sex-ratio selection. Thus, we explain the observed pattern of genome elimination. Our results highlight the interaction between mating system, sex-ratio selection and intragenomic conflict.

  1. PAR polarity: from complexity to design principles.

    PubMed

    Goehring, Nathan W

    2014-11-01

    The par-titioning-defective or PAR proteins comprise the core of an essential cell polarity network that underlies polarization in a wide variety of cell types and developmental contexts. The output of this network in nearly every case is the establishment of opposing and complementary membrane domains that define a cell׳s polarity axis. Yet, behind this simple pattern is a complex system of interactions, regulation and dynamic behaviors. How these various parts combine to generate polarized patterns of protein localization in cells is only beginning to become clear. This review, part of the Special Issue on Cell Polarity, aims to highlight several emerging themes and design principles that underlie the process of cell polarization by components of the PAR network. PMID:25128809

  2. Humanizing the Protease-Activated Receptor (PAR) Expression Profile in Mouse Platelets by Knocking PAR1 into the Par3 Locus Reveals PAR1 Expression Is Not Tolerated in Mouse Platelets

    PubMed Central

    French, Shauna L.; Paramitha, Antonia C.; Moon, Mitchell J.; Dickins, Ross A.; Hamilton, Justin R.

    2016-01-01

    Anti-platelet drugs are the mainstay of pharmacotherapy for heart attack and stroke prevention, yet improvements are continually sought. Thrombin is the most potent activator of platelets and targeting platelet thrombin receptors (protease-activated receptors; PARs) is an emerging anti-thrombotic approach. Humans express two PARs on their platelets–PAR1 and PAR4. The first PAR1 antagonist was recently approved for clinical use and PAR4 antagonists are in early clinical development. However, pre-clinical studies examining platelet PAR function are challenging because the platelets of non-primates do not accurately reflect the PAR expression profile of human platelets. Mice, for example, express Par3 and Par4. To address this limitation, we aimed to develop a genetically modified mouse that would express the same repertoire of platelet PARs as humans. Here, human PAR1 preceded by a lox-stop-lox was knocked into the mouse Par3 locus, and then expressed in a platelet-specific manner (hPAR1-KI mice). Despite correct targeting and the predicted loss of Par3 expression and function in platelets from hPAR1-KI mice, no PAR1 expression or function was detected. Specifically, PAR1 was not detected on the platelet surface nor internally by flow cytometry nor in whole cell lysates by Western blot, while a PAR1-activating peptide failed to induce platelet activation assessed by either aggregation or surface P-selectin expression. Platelets from hPAR1-KI mice did display significantly diminished responsiveness to thrombin stimulation in both assays, consistent with a Par3-/- phenotype. In contrast to the observations in hPAR1-KI mouse platelets, the PAR1 construct used here was successfully expressed in HEK293T cells. Together, these data suggest ectopic PAR1 expression is not tolerated in mouse platelets and indicate a different approach is required to develop a small animal model for the purpose of any future preclinical testing of PAR antagonists as anti-platelet drugs. PMID

  3. A DFT study on the NHC catalysed Michael addition of enols to α,β-unsaturated acyl-azoliums. A base catalysed C-C bond-formation step.

    PubMed

    Domingo, Luis R; Sáez, José A; Arnó, Manuel

    2014-02-14

    The NHC catalysed nucleophilic additions of enols to α,β-unsaturated acyl-azolium intermediates have been investigated using DFT methods at the MPWB1K/6-31G** computational level. In the direct and the conjugate additions, formation of a hydrogen bond (HB) with the carboxyl oxygen is not sufficient to favour the C-C bond formation as a consequence of the low nucleophilic character of enols. Interestingly, when enols form a HB with the chloride counterion, the activation energies associated with the conjugate addition decrease as a consequence of the increased nucleophilic character of enols and the increased electrophilic character of the 'acyl-azolium + Cl' ion pair. Analysis of the DFT reactivity indices allows establishing a base catalysed C-C bond-formation step promoted by the chloride counterion. PMID:24343422

  4. A DFT study on the NHC catalysed Michael addition of enols to α,β-unsaturated acyl-azoliums. A base catalysed C-C bond-formation step.

    PubMed

    Domingo, Luis R; Sáez, José A; Arnó, Manuel

    2014-02-14

    The NHC catalysed nucleophilic additions of enols to α,β-unsaturated acyl-azolium intermediates have been investigated using DFT methods at the MPWB1K/6-31G** computational level. In the direct and the conjugate additions, formation of a hydrogen bond (HB) with the carboxyl oxygen is not sufficient to favour the C-C bond formation as a consequence of the low nucleophilic character of enols. Interestingly, when enols form a HB with the chloride counterion, the activation energies associated with the conjugate addition decrease as a consequence of the increased nucleophilic character of enols and the increased electrophilic character of the 'acyl-azolium + Cl' ion pair. Analysis of the DFT reactivity indices allows establishing a base catalysed C-C bond-formation step promoted by the chloride counterion.

  5. Metal-catalysed azidation of tertiary C-H bonds suitable for late-stage functionalization.

    PubMed

    Sharma, Ankit; Hartwig, John F

    2015-01-29

    Many enzymes oxidize unactivated aliphatic C-H bonds selectively to form alcohols; however, biological systems do not possess enzymes that catalyse the analogous aminations of C-H bonds. The absence of such enzymes limits the discovery of potential medicinal candidates because nitrogen-containing groups are crucial to the biological activity of therapeutic agents and clinically useful natural products. In one prominent example illustrating the importance of incorporating nitrogen-based functionality, the conversion of the ketone of erythromycin to the -N(Me)CH2- group in azithromycin leads to a compound that can be dosed once daily with a shorter treatment time. For such reasons, synthetic chemists have sought catalysts that directly convert C-H bonds to C-N bonds. Most currently used catalysts for C-H bond amination are ill suited to the intermolecular functionalization of complex molecules because they require excess substrate or directing groups, harsh reaction conditions, weak or acidic C-H bonds, or reagents containing specialized groups on the nitrogen atom. Among C-H bond amination reactions, those forming a C-N bond at a tertiary alkyl group would be particularly valuable, because this linkage is difficult to form from ketones or alcohols that might be created in a biosynthetic pathway by oxidation. Here we report a mild, selective, iron-catalysed azidation of tertiary C-H bonds that occurs without excess of the valuable substrate. The reaction tolerates aqueous environments and is suitable for the functionalization of complex structures in the late stages of a multistep synthesis. Moreover, this azidation makes it possible to install a range of nitrogen-based functional groups, including those from Huisgen 'click' cycloadditions and the Staudinger ligation. We anticipate that these reactions will create opportunities to modify natural products, their precursors and their derivatives to produce analogues that contain different polarity and charge as a

  6. Metal-catalysed azidation of tertiary C-H bonds suitable for late-stage functionalization

    NASA Astrophysics Data System (ADS)

    Sharma, Ankit; Hartwig, John F.

    2015-01-01

    Many enzymes oxidize unactivated aliphatic C-H bonds selectively to form alcohols; however, biological systems do not possess enzymes that catalyse the analogous aminations of C-H bonds. The absence of such enzymes limits the discovery of potential medicinal candidates because nitrogen-containing groups are crucial to the biological activity of therapeutic agents and clinically useful natural products. In one prominent example illustrating the importance of incorporating nitrogen-based functionality, the conversion of the ketone of erythromycin to the -N(Me)CH2- group in azithromycin leads to a compound that can be dosed once daily with a shorter treatment time. For such reasons, synthetic chemists have sought catalysts that directly convert C-H bonds to C-N bonds. Most currently used catalysts for C-H bond amination are ill suited to the intermolecular functionalization of complex molecules because they require excess substrate or directing groups, harsh reaction conditions, weak or acidic C-H bonds, or reagents containing specialized groups on the nitrogen atom. Among C-H bond amination reactions, those forming a C-N bond at a tertiary alkyl group would be particularly valuable, because this linkage is difficult to form from ketones or alcohols that might be created in a biosynthetic pathway by oxidation. Here we report a mild, selective, iron-catalysed azidation of tertiary C-H bonds that occurs without excess of the valuable substrate. The reaction tolerates aqueous environments and is suitable for the functionalization of complex structures in the late stages of a multistep synthesis. Moreover, this azidation makes it possible to install a range of nitrogen-based functional groups, including those from Huisgen `click' cycloadditions and the Staudinger ligation. We anticipate that these reactions will create opportunities to modify natural products, their precursors and their derivatives to produce analogues that contain different polarity and charge as a

  7. ParA and ParB coordinate chromosome segregation with cell elongation and division during Streptomyces sporulation

    PubMed Central

    Donczew, Magdalena; Mackiewicz, Paweł; Wróbel, Agnieszka; Flärdh, Klas; Zakrzewska-Czerwińska, Jolanta

    2016-01-01

    In unicellular bacteria, the ParA and ParB proteins segregate chromosomes and coordinate this process with cell division and chromosome replication. During sporulation of mycelial Streptomyces, ParA and ParB uniformly distribute multiple chromosomes along the filamentous sporogenic hyphal compartment, which then differentiates into a chain of unigenomic spores. However, chromosome segregation must be coordinated with cell elongation and multiple divisions. Here, we addressed the question of whether ParA and ParB are involved in the synchronization of cell-cycle processes during sporulation in Streptomyces. To answer this question, we used time-lapse microscopy, which allows the monitoring of growth and division of single sporogenic hyphae. We showed that sporogenic hyphae stop extending at the time of ParA accumulation and Z-ring formation. We demonstrated that both ParA and ParB affect the rate of hyphal extension. Additionally, we showed that ParA promotes the formation of massive nucleoprotein complexes by ParB. We also showed that FtsZ ring assembly is affected by the ParB protein and/or unsegregated DNA. Our results indicate the existence of a checkpoint between the extension and septation of sporogenic hyphae that involves the ParA and ParB proteins. PMID:27248800

  8. Clause Elimination Procedures for CNF Formulas

    NASA Astrophysics Data System (ADS)

    Heule, Marijn; Järvisalo, Matti; Biere, Armin

    We develop and analyze clause elimination procedures, a specific family of simplification techniques for conjunctive normal form (CNF) formulas. Extending known procedures such as tautology, subsumption, and blocked clause elimination, we introduce novel elimination procedures based on hidden and asymmetric variants of these techniques. We analyze the resulting nine (including five new) clause elimination procedures from various perspectives: size reduction, BCP-preservance, confluence, and logical equivalence. For the variants not preserving logical equivalence, we show how to reconstruct solutions to original CNFs from satisfying assignments to simplified CNFs. We also identify a clause elimination procedure that does a transitive reduction of the binary implication graph underlying any CNF formula purely on the CNF level.

  9. Plasmin-dependent elimination of the growth-factor-like domain in urokinase causes its rapid cellular uptake and degradation.

    PubMed Central

    Poliakov, A; Tkachuk, V; Ovchinnikova, T; Potapenko, N; Bagryantsev, S; Stepanova, V

    2001-01-01

    Urokinase-type plasminogen activator (uPA) and its receptor (uPAR) act in concert to mediate pericellular proteolysis and to stimulate intracellular signalling responsible for cell migration and proliferation. uPA is composed of three domains, a proteolytic domain (PD), a kringle domain (KD) and a growth-factor-like domain (GFD), the last of which mediates the interaction with uPAR. We demonstrate that uPA, associated with the surface of U937 cells, undergoes plasmin-mediated cleavage of the Lys(46)-Ser(47) bond with elimination of the GFD. Using recombinant forms of uPA, we show that a uPA variant lacking the GFD (r-uPADeltaGFD) and unable to associate with uPAR is rapidly cleared from the cell surface. Binding and internalization of r-uPADeltaGFD are markedly decreased in the presence of 39 kDa receptor-associated protein (RAP), the antagonist of several endocytic receptors of the low-density lipoprotein receptor family, suggesting that this protein clearance pathway is used for r-uPADeltaGFD. In contrast with rapidly internalized r-uPADeltaGFD, the intact recombinant single-chain urokinase with wild-type structure (r-uPAwt) bound to uPAR is retained on the cell surface. Soluble uPAR protects uPA from cleavage by plasmin that results in the elimination of GFD, suggesting that uPAR might protect cell-bound urokinase from plasmin-mediated cleavage between the GFD and KD and subsequent degradation. PMID:11311125

  10. Silver-catalysed azide-alkyne cycloaddition (AgAAC): assessing the mechanism by density functional theory calculations

    NASA Astrophysics Data System (ADS)

    Banerji, Biswadip; Chandrasekhar, K.; Killi, Sunil Kumar; Pramanik, Sumit Kumar; Uttam, Pal; Sen, Sudeshna; Maiti, Nakul Chandra

    2016-09-01

    `Click reactions' are the copper catalysed dipolar cycloaddition reaction of azides and alkynes to incorporate nitrogens into a cyclic hydrocarbon scaffold forming a triazole ring. Owing to its efficiency and versatility, this reaction and the products, triazole-containing heterocycles, have immense importance in medicinal chemistry. Copper is the only known catalyst to carry out this reaction, the mechanism of which remains unclear. We report here that the `click reactions' can also be catalysed by silver halides in non-aqueous medium. It constitutes an alternative to the well-known CuAAC click reaction. The yield of the reaction varies on the type of counter ion present in the silver salt. This reaction exhibits significant features, such as high regioselectivity, mild reaction conditions, easy availability of substrates and reasonably good yields. In this communication, the findings of a new catalyst along with the effect of solvent and counter ions will help to decipher the still obscure mechanism of this important reaction.

  11. Rapid assembly of functionalised spirocyclic indolines by palladium-catalysed dearomatising diallylation of indoles with allyl acetate.

    PubMed

    Dhankher, Persis; Benhamou, Laure; Sheppard, Tom D

    2014-10-01

    Herein, we report the application of allyl acetate to the palladium-catalysed dearomatising diallylation of indoles. The reaction can be carried out by using a readily available palladium catalyst at room temperature, and can be applied to a wide range of substituted indoles to provide access to the corresponding 3,3-diallylindolinines. These compounds are versatile synthetic intermediates that readily undergo Ugi reactions or proline-catalysed asymmetric Mannich reactions. Alternatively, acylation of the 3,3-diallylindolinines with an acid chloride or a chloroformate, followed by treatment with aluminium chloride, enables 2,3-diallylindoles to be prepared. By using ring-closing metathesis, functionalised spirocyclic indoline scaffolds can be accessed from the Ugi products, and a dihydrocarbazole can be prepared from the corresponding 2,3-diallylindole.

  12. suPAR and Team Nephrology

    PubMed Central

    2014-01-01

    Primary focal segmental glomerulosclerosis (FSGS) accounts for nearly 10 % of patients who require renal replacement therapy. Elevated circulating levels of soluble urokinase receptor (suPAR) have been identified as a biomarker to discriminate primary FSGS from other glomerulopathies. Subsequent reports have questioned the diagnostic utility of this test. In a study in BMC Medicine, Huang et al. demonstrate that urinary soluble urokinase receptor (suPAR) excretion assists in distinguishing primary FSGS from other glomerular diseases, and that high plasma suPAR concentrations are not directly linked to a decline in glomerular filtration rate (GFR). This observation suggests that further investigation of suPAR is warranted in patients with FSGS. It should be interpreted in light of a recent report that B7-1 is expressed in the podocytes of a subset of patients with FSGS, and that blocking this molecule may represent the first successful targeted intervention for this disease. These advances highlight the rapid pace of scientific progress in the field of nephrology. Nephrologists should work together, share resources, and expedite the design of protocols to evaluate these novel biomarkers in a comprehensive and scientifically valid manner. Please see related article http://www.biomedcentral.com/1741-7015/12/81. PMID:24885021

  13. Gold-catalysed cross-coupling between aryldiazonium salts and arylboronic acids: probing the usefulness of photoredox conditions.

    PubMed

    Cornilleau, Thomas; Hermange, Philippe; Fouquet, Eric

    2016-08-21

    The synthesis of biaryl compounds from aryldiazonium salts and arylboronic acids was achieved using PPh3AuCl as catalyst, CsF as base and acetonitrile as solvent. Combined to photosensitizers, irradiation by blue LEDs allowed accelerating the reaction and expanding its scope. Various functional groups were compatible including bromoaryls, iodoaryls, aldehydes and alcohols. A 2-iodobenzyl alcohol moiety was smoothly introduced by this method, enabling its consecutive isotopic labelling by a Pd-catalysed alkoxycarbonylation. PMID:27452177

  14. Synthesis of 11C labelled methyl esters: transesterification of enol esters versus BF 3 catalysed esterification—a comparative study

    NASA Astrophysics Data System (ADS)

    Ackermann, Uwe; Blanc, Paul; Falzon, Cheryl L.; Issa, William; White, Jonathan; Tochon-Danguy, Henri J.; Sachinidis, John I.; Scott, Andrew M.

    2006-01-01

    C-11 labelled methyl esters have been synthesized via the transesterification of enol esters in the presence of C-11 methanol and 1,3 dichlorodibutylstannoxane as catalyst. This method leaves functional groups intact and allows access to a wider variety of C-11 labelled methyl esters compared to the BF 3 catalysed ester formation, which uses carboxylic acids and C-11 methanol as starting materials.

  15. Chemoenzymatic one-pot synthesis in an aqueous medium: combination of metal-catalysed allylic alcohol isomerisation-asymmetric bioamination.

    PubMed

    Ríos-Lombardía, Nicolás; Vidal, Cristian; Cocina, María; Morís, Francisco; García-Álvarez, Joaquín; González-Sabín, Javier

    2015-07-11

    The ruthenium-catalysed isomerisation of allylic alcohols was coupled, for the first time, with asymmetric bioamination in a one-pot process in an aqueous medium. In the cases involving prochiral ketones, the ω-TA exhibited excellent enantioselectivity, identical to that observed in the single step. As a result, amines were obtained from allylic alcohols with high overall yields and excellent enantiomeric excesses.

  16. Laccase‐catalysed oxidations of naturally occurring phenols: from in vivo biosynthetic pathways to green synthetic applications

    PubMed Central

    Jeon, Jong‐Rok; Baldrian, Petr; Murugesan, Kumarasamy; Chang, Yoon‐Seok

    2012-01-01

    Summary Laccases are oxidases that contain several copper atoms, and catalyse single‐electron oxidations of phenolic compounds with concomitant reduction of oxygen to water. The enzymes are particularly widespread in ligninolytic basidiomycetes, but also occur in certain prokaryotes, insects and plants. Depending on the species, laccases are involved in various biosynthetic processes contributing to carbon recycling in land ecosystems and the morphogenesis of biomatrices, wherein low‐molecular‐weight naturally occurring phenols serve as key enzyme substrates. Studies of these in vivo synthetic pathways have afforded new insights into fungal laccase applicability in green synthetic chemistry. Thus, we here review fungal laccase‐catalysed oxidations of naturally occurring phenols that are particularly relevant to the synthesis of fine organic chemicals, and we discuss how the discovered synthetic strategies mimic laccase‐involved in vivo pathways, thus enhancing the green nature of such reactions. Laccase‐catalysed in vivo processes yield several types of biopolymers, including those of cuticles, lignin, polyflavonoids, humus and the melanin pigments, using natural mono‐ or poly‐phenols as building blocks. The in vivo synthetic pathways involve either phenoxyl radical‐mediated coupling or cross‐linking reactions, and can be adapted to the design of in vitro oxidative processes involving fungal laccases in organic synthesis; the laccase substrates and the synthetic mechanisms reflect in vivo processes. Notably, such in vitro synthetic pathways can also reproduce physicochemical properties (e.g. those of chromophores, and radical‐scavenging, hydration and antimicrobial activities) found in natural biomaterials. Careful study of laccase‐associated in vivo metabolic pathways has been rewarded by the discovery of novel green applications for fungal laccases. This review comprehensively summarizes the available data on laccase‐catalysed

  17. Spirochaete flagella hook proteins self-catalyse a lysinoalanine covalent crosslink for motility.

    PubMed

    Miller, Michael R; Miller, Kelly A; Bian, Jiang; James, Milinda E; Zhang, Sheng; Lynch, Michael J; Callery, Patrick S; Hettick, Justin M; Cockburn, Andrew; Liu, Jun; Li, Chunhao; Crane, Brian R; Charon, Nyles W

    2016-01-01

    Spirochaetes are bacteria responsible for several serious diseases, including Lyme disease (Borrelia burgdorferi), syphilis (Treponema pallidum) and leptospirosis (Leptospira interrogans), and contribute to periodontal diseases (Treponema denticola)(1). These spirochaetes employ an unusual form of flagella-based motility necessary for pathogenicity; indeed, spirochaete flagella (periplasmic flagella) reside and rotate within the periplasmic space(2-11). The universal joint or hook that links the rotary motor to the filament is composed of ∼120-130 FlgE proteins, which in spirochaetes form an unusually stable, high-molecular-weight complex(9,12-17). In other bacteria, the hook can be readily dissociated by treatments such as heat(18). In contrast, spirochaete hooks are resistant to these treatments, and several lines of evidence indicate that the high-molecular-weight complex is the consequence of covalent crosslinking(12,13,17). Here, we show that T. denticola FlgE self-catalyses an interpeptide crosslinking reaction between conserved lysine and cysteine, resulting in the formation of an unusual lysinoalanine adduct that polymerizes the hook subunits. Lysinoalanine crosslinks are not needed for flagellar assembly, but they are required for cell motility and hence infection. The self-catalytic nature of FlgE crosslinking has important implications for protein engineering, and its sensitivity to chemical inhibitors provides a new avenue for the development of antimicrobials targeting spirochaetes. PMID:27670115

  18. Synthesis of deuterium-labelled halogen derivatives of L-tryptophan catalysed by tryptophanase.

    PubMed

    Winnicka, Elżbieta; Szymańska, Jolanta; Kańska, Marianna

    2016-06-01

    The isotopomers of halogen derivatives of l-tryptophan (l-Trp) (4'-F-, 7'-F-, 5'-Cl- and 7'-Br-l-Trp), specifically labelled with deuterium in α-position of the side chain, were obtained by enzymatic coupling of the corresponding halogenated derivatives of indole with S-methyl-l-cysteine in (2)H2O, catalysed by enzyme tryptophanase (EC 4.1.99.1). The positional deuterium enrichment of the resulting tryptophan derivatives was controlled using (1)H NMR. In accordance with the mechanism of the lyase reaction, a 100% deuterium labelling was observed in the α-position; the chemical yields were between 23 and 51%. Furthermore, β-F-l-alanine, synthesized from β-F-pyruvic acid by the l-alanine dehydrogenase reaction, has been tested as a coupling agent to obtain the halogenated deuterium-labelled derivatives of l-Trp. The chemical yield (∼30%) corresponded to that as observed with S-methyl-l-cysteine but the deuterium label was only 63%, probably due to the use of a not completely deuterated incubation medium.

  19. Vanillin formation from ferulic acid in Vanilla planifolia is catalysed by a single enzyme

    PubMed Central

    Gallage, Nethaji J.; Hansen, Esben H.; Kannangara, Rubini; Olsen, Carl Erik; Motawia, Mohammed Saddik; Jørgensen, Kirsten; Holme, Inger; Hebelstrup, Kim; Grisoni, Michel; Møller, Birger Lindberg

    2014-01-01

    Vanillin is a popular and valuable flavour compound. It is the key constituent of the natural vanilla flavour obtained from cured vanilla pods. Here we show that a single hydratase/lyase type enzyme designated vanillin synthase (VpVAN) catalyses direct conversion of ferulic acid and its glucoside into vanillin and its glucoside, respectively. The enzyme shows high sequence similarity to cysteine proteinases and is specific to the substitution pattern at the aromatic ring and does not metabolize caffeic acid and p-coumaric acid as demonstrated by coupled transcription/translation assays. VpVAN localizes to the inner part of the vanilla pod and high transcript levels are found in single cells located a few cell layers from the inner epidermis. Transient expression of VpVAN in tobacco and stable expression in barley in combination with the action of endogenous alcohol dehydrogenases and UDP-glucosyltransferases result in vanillyl alcohol glucoside formation from endogenous ferulic acid. A gene encoding an enzyme showing 71% sequence identity to VpVAN was identified in another vanillin-producing plant species Glechoma hederacea and was also shown to be a vanillin synthase as demonstrated by transient expression in tobacco. PMID:24941968

  20. Characterization of uronate dehydrogenases catalysing the initial step in an oxidative pathway

    PubMed Central

    Pick, André; Schmid, Jochen; Sieber, Volker

    2015-01-01

    Uronate dehydrogenases catalyse the oxidation of uronic acids to aldaric acids, which represent ‘top value-added chemicals’ that have the potential to substitute petroleum-derived chemicals. The identification and annotation of three uronate dehydrogenases derived from Fulvimarina pelagi HTCC2506, Streptomyces viridochromogenes DSM 40736 and Oceanicola granulosus DSM 15982 via sequence analysis is described. Characterization and comparison with two known uronate dehydrogenases in regard to substrate spectrum, catalytic activity and pH as well as temperature dependence was performed. The catalytic efficiency was investigated in two different buffer systems; potassium phosphate and Tris-HCl. In addition to the typical and well available substrates glucuronate and galacturonate also mannuronate as part of many structural polysaccharides were tested. The uronate dehydrogenase of Agrobacterium tumefaciens and Pseudomonas syringae showed catalytic dependency on the buffer system resulting in an increased Km especially for glucuronate in potassium phosphate compared with Tris-HCl buffer. Enzyme stability at 37°C of the different Udhs was in the order: P. syringae < S. viridochromogens < A. tumefaciens < F. pelagi < O. granulosus. All enzymes showed activity within a broad pH range from 7.0 to 9.5, only O. granulosus had a very narrow range around 7.0. PMID:25884328

  1. Acid-catalysed xylose dehydration into furfural in the presence of kraft lignin.

    PubMed

    Lamminpää, Kaisa; Ahola, Juha; Tanskanen, Juha

    2015-02-01

    In this study, the effects of kraft lignin (Indulin AT) on acid-catalysed xylose dehydration into furfural were studied in formic and sulphuric acids. The study was done using D-optimal design. Three variables in both acids were included in the design: time (20-80 min), temperature (160-180°C) and initial lignin concentration (0-20 g/l). The dependent variables were xylose conversion, furfural yield, furfural selectivity and pH change. The results showed that the xylose conversion and furfural yield decreased in sulphuric acid, while in formic acid the changes were minor. Additionally, it was showed that lignin has an acid-neutralising capacity, and the added lignin increased the pH of reactant solutions in both acids. The pH rise was considerably lower in formic acid than in sulphuric acid. However, the higher pH did not explain all the changes in conversion and yield, and thus lignin evidently inhibits the formation of furfural.

  2. Palladium-catalysed transannular C-H functionalization of alicyclic amines

    NASA Astrophysics Data System (ADS)

    Topczewski, Joseph J.; Cabrera, Pablo J.; Saper, Noam I.; Sanford, Melanie S.

    2016-03-01

    Discovering pharmaceutical candidates is a resource-intensive enterprise that frequently requires the parallel synthesis of hundreds or even thousands of molecules. C-H bonds are present in almost all pharmaceutical agents. Consequently, the development of selective, rapid and efficient methods for converting these bonds into new chemical entities has the potential to streamline pharmaceutical development. Saturated nitrogen-containing heterocycles (alicyclic amines) feature prominently in pharmaceuticals, such as treatments for depression (paroxetine, amitifadine), diabetes (gliclazide), leukaemia (alvocidib), schizophrenia (risperidone, belaperidone), malaria (mefloquine) and nicotine addiction (cytisine, varenicline). However, existing methods for the C-H functionalization of saturated nitrogen heterocycles, particularly at sites remote to nitrogen, remain extremely limited. Here we report a transannular approach to selectively manipulate the C-H bonds of alicyclic amines at sites remote to nitrogen. Our reaction uses the boat conformation of the substrates to achieve palladium-catalysed amine-directed conversion of C-H bonds to C-C bonds on various alicyclic amine scaffolds. We demonstrate this approach by synthesizing new derivatives of several bioactive molecules, including varenicline.

  3. Chemical synthesis of lactic acid from cellulose catalysed by lead(II) ions in water.

    PubMed

    Wang, Yanliang; Deng, Weiping; Wang, Binju; Zhang, Qinghong; Wan, Xiaoyue; Tang, Zhenchen; Wang, Ye; Zhu, Chun; Cao, Zexing; Wang, Guichang; Wan, Huilin

    2013-01-01

    The direct transformation of cellulose, which is the main component of lignocellulosic biomass, into building-block chemicals is the key to establishing biomass-based sustainable chemical processes. Only limited successes have been achieved for such transformations under mild conditions. Here we report the simple and efficient chemocatalytic conversion of cellulose in water in the presence of dilute lead(II) ions, into lactic acid, which is a high-value chemical used for the production of fine chemicals and biodegradable plastics. The lactic acid yield from microcrystalline cellulose and several lignocellulose-based raw biomasses is >60% at 463 K. Both theoretical and experimental studies suggest that lead(II) in combination with water catalyses a series of cascading steps for lactic acid formation, including the isomerization of glucose formed via the hydrolysis of cellulose into fructose, the selective cleavage of the C3-C4 bond of fructose to trioses and the selective conversion of trioses into lactic acid. PMID:23846730

  4. Vanillin formation from ferulic acid in Vanilla planifolia is catalysed by a single enzyme.

    PubMed

    Gallage, Nethaji J; Hansen, Esben H; Kannangara, Rubini; Olsen, Carl Erik; Motawia, Mohammed Saddik; Jørgensen, Kirsten; Holme, Inger; Hebelstrup, Kim; Grisoni, Michel; Møller, Birger Lindberg

    2014-01-01

    Vanillin is a popular and valuable flavour compound. It is the key constituent of the natural vanilla flavour obtained from cured vanilla pods. Here we show that a single hydratase/lyase type enzyme designated vanillin synthase (VpVAN) catalyses direct conversion of ferulic acid and its glucoside into vanillin and its glucoside, respectively. The enzyme shows high sequence similarity to cysteine proteinases and is specific to the substitution pattern at the aromatic ring and does not metabolize caffeic acid and p-coumaric acid as demonstrated by coupled transcription/translation assays. VpVAN localizes to the inner part of the vanilla pod and high transcript levels are found in single cells located a few cell layers from the inner epidermis. Transient expression of VpVAN in tobacco and stable expression in barley in combination with the action of endogenous alcohol dehydrogenases and UDP-glucosyltransferases result in vanillyl alcohol glucoside formation from endogenous ferulic acid. A gene encoding an enzyme showing 71% sequence identity to VpVAN was identified in another vanillin-producing plant species Glechoma hederacea and was also shown to be a vanillin synthase as demonstrated by transient expression in tobacco. PMID:24941968

  5. Effect of metal ions on the kinetics of tyrosine oxidation catalysed by tyrosinase.

    PubMed

    Palumbo, A; Misuraca, G; D'Ischia, M; Prota, G

    1985-06-15

    The conversion of tyrosine into dopa [3-(3,4-dihydroxyphenyl)alanine] is the rate limiting step in the biosynthesis of melanins catalysed by tyrosinase. This hydroxylation reaction is characterized by a lag period, the extent of which depends on various parameters, notably the presence of a suitable hydrogen donor such as dopa or tetrahydropterin. We have now found that catalytic amounts of Fe2+ ions have the same effect as dopa in stimulating the tyrosine hydroxylase activity of the enzyme. Kinetic experiments showed that the shortening of the induction time depends on the concentration of the added metal and the nature of the buffer system used and is not suppressed by superoxide dismutase, catalase, formate or mannitol. Notably, Fe3+ ions showed only a small delaying effect on tyrosinase activity. Among the other metals which were tested, Zn2+, Co2+, Cd2+ and Ni2+ had no detectable influence, whereas Cu2+ and Mn2+ exhibited a marked inhibitory effect on the kinetics of tyrosine oxidation. These findings are discussed in the light of the commonly accepted mechanism of action of tyrosinase. PMID:3927896

  6. Sequence-defined bioactive macrocycles via an acid-catalysed cascade reaction

    NASA Astrophysics Data System (ADS)

    Porel, Mintu; Thornlow, Dana N.; Phan, Ngoc N.; Alabi, Christopher A.

    2016-06-01

    Synthetic macrocycles derived from sequence-defined oligomers are a unique structural class whose ring size, sequence and structure can be tuned via precise organization of the primary sequence. Similar to peptides and other peptidomimetics, these well-defined synthetic macromolecules become pharmacologically relevant when bioactive side chains are incorporated into their primary sequence. In this article, we report the synthesis of oligothioetheramide (oligoTEA) macrocycles via a one-pot acid-catalysed cascade reaction. The versatility of the cyclization chemistry and modularity of the assembly process was demonstrated via the synthesis of >20 diverse oligoTEA macrocycles. Structural characterization via NMR spectroscopy revealed the presence of conformational isomers, which enabled the determination of local chain dynamics within the macromolecular structure. Finally, we demonstrate the biological activity of oligoTEA macrocycles designed to mimic facially amphiphilic antimicrobial peptides. The preliminary results indicate that macrocyclic oligoTEAs with just two-to-three cationic charge centres can elicit potent antibacterial activity against Gram-positive and Gram-negative bacteria.

  7. Vanillin formation from ferulic acid in Vanilla planifolia is catalysed by a single enzyme.

    PubMed

    Gallage, Nethaji J; Hansen, Esben H; Kannangara, Rubini; Olsen, Carl Erik; Motawia, Mohammed Saddik; Jørgensen, Kirsten; Holme, Inger; Hebelstrup, Kim; Grisoni, Michel; Møller, Birger Lindberg

    2014-06-19

    Vanillin is a popular and valuable flavour compound. It is the key constituent of the natural vanilla flavour obtained from cured vanilla pods. Here we show that a single hydratase/lyase type enzyme designated vanillin synthase (VpVAN) catalyses direct conversion of ferulic acid and its glucoside into vanillin and its glucoside, respectively. The enzyme shows high sequence similarity to cysteine proteinases and is specific to the substitution pattern at the aromatic ring and does not metabolize caffeic acid and p-coumaric acid as demonstrated by coupled transcription/translation assays. VpVAN localizes to the inner part of the vanilla pod and high transcript levels are found in single cells located a few cell layers from the inner epidermis. Transient expression of VpVAN in tobacco and stable expression in barley in combination with the action of endogenous alcohol dehydrogenases and UDP-glucosyltransferases result in vanillyl alcohol glucoside formation from endogenous ferulic acid. A gene encoding an enzyme showing 71% sequence identity to VpVAN was identified in another vanillin-producing plant species Glechoma hederacea and was also shown to be a vanillin synthase as demonstrated by transient expression in tobacco.

  8. Graphitic platform for self-catalysed InAs nanowires growth by molecular beam epitaxy

    PubMed Central

    2014-01-01

    We report the self-catalysed growth of InAs nanowires (NWs) on graphite thin films using molecular beam epitaxy via a droplet-assisted technique. Through optimising metal droplets, we obtained vertically aligned InAs NWs with highly uniform diameter along their entire length. In comparison with conventional InAs NWs grown on Si (111), the graphite surface led to significant effects on the NWs geometry grown on it, i.e. larger diameter, shorter length with lower number density, which were ascribed to the absence of dangling bonds on the graphite surface. The axial growth rate of the NWs has a strong dependence on growth time, which increases quickly in the beginning then slows down after the NWs reach a length of approximately 0.8 μm. This is attributed to the combined axial growth contributions from the surface impingement and sidewall impingement together with the desorption of adatoms during the diffusion. The growth of InAs NWs on graphite was proposed following a vapour-solid mechanism. High-resolution transmission electron microscopy reveals that the NW has a mixture of pure zinc-blende and wurtzite insertions. PMID:25024683

  9. Epoxidation of olefins catalysed by vanadium-salan complexes: a theoretical mechanistic study.

    PubMed

    Kuznetsov, Maxim L; Pessoa, João Costa

    2009-07-28

    Plausible mechanisms of olefin epoxidation catalysed by a V-salan model complex [VIV(=O)(L)(H2O)] (1, L=(CH2NHCH2CH=CHO-)2) in the presence of H2O2 are investigated and compared by theoretical methods using density functional theory. Three main routes, i.e. the Mimoun, Sharpless and biradical mechanisms, were examined in detail, and the Sharpless pathway was found to be the most favourable one. The reaction starts from the formation of an active catalytic species [VV(=O)(OO)(LH)] (3c) upon interaction of 1 with H2O2, then concerted, highly synchronous attack of the olefin to 3c occurs yielding the epoxide and catalyst [VV(=O)2(LH)], the latter being oxidized by H2O2 to 3c. The activation barrier strongly depends on the proton location in the catalyst molecule and is the lowest when one of the oxygen atoms of the salan ligand is protonated and the vanadium atom is penta-coordinated with one vacant coordination position (complex 3c). The olefin in this reaction acts as an electron donor (nucleophile) rather than as an electron acceptor (electrophile). PMID:19587988

  10. Palladium-catalysed transannular C-H functionalization of alicyclic amines.

    PubMed

    Topczewski, Joseph J; Cabrera, Pablo J; Saper, Noam I; Sanford, Melanie S

    2016-03-10

    Discovering pharmaceutical candidates is a resource-intensive enterprise that frequently requires the parallel synthesis of hundreds or even thousands of molecules. C-H bonds are present in almost all pharmaceutical agents. Consequently, the development of selective, rapid and efficient methods for converting these bonds into new chemical entities has the potential to streamline pharmaceutical development. Saturated nitrogen-containing heterocycles (alicyclic amines) feature prominently in pharmaceuticals, such as treatments for depression (paroxetine, amitifadine), diabetes (gliclazide), leukaemia (alvocidib), schizophrenia (risperidone, belaperidone), malaria (mefloquine) and nicotine addiction (cytisine, varenicline). However, existing methods for the C-H functionalization of saturated nitrogen heterocycles, particularly at sites remote to nitrogen, remain extremely limited. Here we report a transannular approach to selectively manipulate the C-H bonds of alicyclic amines at sites remote to nitrogen. Our reaction uses the boat conformation of the substrates to achieve palladium-catalysed amine-directed conversion of C-H bonds to C-C bonds on various alicyclic amine scaffolds. We demonstrate this approach by synthesizing new derivatives of several bioactive molecules, including varenicline.

  11. Extraction of copper from an oxidized (lateritic) ore using bacterially catalysed reductive dissolution.

    PubMed

    Nancucheo, Ivan; Grail, Barry M; Hilario, Felipe; du Plessis, Chris; Johnson, D Barrie

    2014-01-01

    An oxidized lateritic ore which contained 0.8 % (by weight) copper was bioleached in pH- and temperature-controlled stirred reactors under acidic reducing conditions using pure and mixed cultures of the acidophilic chemolithotrophic bacterium Acidithiobacillus ferrooxidans. Sulfur was provided as the electron donor for the bacteria, and ferric iron present in goethite (the major ferric iron mineral present in the ore) acted as electron acceptor. Significantly more copper was leached by bacterially catalysed reductive dissolution of the laterite than in aerobic cultures or in sterile anoxic reactors, with up to 78 % of the copper present in the ore being extracted. This included copper that was leached from acid-labile minerals (chiefly copper silicates) and that which was associated with ferric iron minerals in the lateritic ore. In the anaerobic bioreactors, soluble iron in the leach liquors was present as iron (II) and copper as copper (I), but both metals were rapidly oxidized (to iron (III) and copper (II)) when the reactors were aerated. The number of bacteria added to the reactors had a critical role in dictating the rate and yield of copper solubilised from the ore. This work has provided further evidence that reductive bioprocessing, a recently described approach for extracting base metals from oxidized deposits, has the potential to greatly extend the range of metal ores that can be biomined. PMID:24687752

  12. Spirochaete flagella hook proteins self-catalyse a lysinoalanine covalent crosslink for motility.

    PubMed

    Miller, Michael R; Miller, Kelly A; Bian, Jiang; James, Milinda E; Zhang, Sheng; Lynch, Michael J; Callery, Patrick S; Hettick, Justin M; Cockburn, Andrew; Liu, Jun; Li, Chunhao; Crane, Brian R; Charon, Nyles W

    2016-08-01

    Spirochaetes are bacteria responsible for several serious diseases, including Lyme disease (Borrelia burgdorferi), syphilis (Treponema pallidum) and leptospirosis (Leptospira interrogans), and contribute to periodontal diseases (Treponema denticola)(1). These spirochaetes employ an unusual form of flagella-based motility necessary for pathogenicity; indeed, spirochaete flagella (periplasmic flagella) reside and rotate within the periplasmic space(2-11). The universal joint or hook that links the rotary motor to the filament is composed of ∼120-130 FlgE proteins, which in spirochaetes form an unusually stable, high-molecular-weight complex(9,12-17). In other bacteria, the hook can be readily dissociated by treatments such as heat(18). In contrast, spirochaete hooks are resistant to these treatments, and several lines of evidence indicate that the high-molecular-weight complex is the consequence of covalent crosslinking(12,13,17). Here, we show that T. denticola FlgE self-catalyses an interpeptide crosslinking reaction between conserved lysine and cysteine, resulting in the formation of an unusual lysinoalanine adduct that polymerizes the hook subunits. Lysinoalanine crosslinks are not needed for flagellar assembly, but they are required for cell motility and hence infection. The self-catalytic nature of FlgE crosslinking has important implications for protein engineering, and its sensitivity to chemical inhibitors provides a new avenue for the development of antimicrobials targeting spirochaetes.

  13. Glycolysis of carbon fiber-epoxy unidirectional mat catalysed by sodium hydroxide

    NASA Astrophysics Data System (ADS)

    Zaini, Mariana Binti Mohd; Badri, Khairiah Haji

    2014-09-01

    This study was conducted to recycle carbon fibre-epoxy (CFRP) composite in woven sheet/ mat form. The CFRP was recycled through glycolysis with polyethlyene glycol (PEG 200) as the solvent. The CFRP was loaded into the solvent at a ratio of 4:1 (w/w). PEG200 was diluted with water to a ratio of 80:20 (v/v). This reaction was catalysed by sodium hydroxide (NaOH) solution with varying concentrations at 1.5, 1.7 and 1.9% (w/v). The glycolysis was conducted at 180-190 °C. The recovered CF (rCF) was analysed using Fourier Transform Infrared (FTIR), Scanning Electron Microscopy (SEM) and Energy Dispersive X-Ray (EDX) while the degraded solution was analysed using FTIR and the epoxy content was determined. The FTIR spectrum of the rCF exhibited the disappearance of the COC peak belonged to epoxy and supported by the SEM micrographs that showed clear rCF. On the other hand, the analysed filtrate detected the disappearance of oxygen peak element in the EDX spectrum for all rCF samples. This gave an indication that the epoxy resin has been removed from the surface of the carbon fiber.

  14. Glycolysis of carbon fiber-epoxy unidirectional mat catalysed by sodium hydroxide

    SciTech Connect

    Zaini, Mariana Binti Mohd; Badri, Khairiah Haji

    2014-09-03

    This study was conducted to recycle carbon fibre-epoxy (CFRP) composite in woven sheet/ mat form. The CFRP was recycled through glycolysis with polyethlyene glycol (PEG 200) as the solvent. The CFRP was loaded into the solvent at a ratio of 4:1 (w/w). PEG200 was diluted with water to a ratio of 80:20 (v/v). This reaction was catalysed by sodium hydroxide (NaOH) solution with varying concentrations at 1.5, 1.7 and 1.9% (w/v). The glycolysis was conducted at 180-190 °C. The recovered CF (rCF) was analysed using Fourier Transform Infrared (FTIR), Scanning Electron Microscopy (SEM) and Energy Dispersive X-Ray (EDX) while the degraded solution was analysed using FTIR and the epoxy content was determined. The FTIR spectrum of the rCF exhibited the disappearance of the COC peak belonged to epoxy and supported by the SEM micrographs that showed clear rCF. On the other hand, the analysed filtrate detected the disappearance of oxygen peak element in the EDX spectrum for all rCF samples. This gave an indication that the epoxy resin has been removed from the surface of the carbon fiber.

  15. Hydrogen tunnelling in enzyme-catalysed H-transfer reactions: flavoprotein and quinoprotein systems

    PubMed Central

    Sutcliffe, Michael J; Masgrau, Laura; Roujeinikova, Anna; Johannissen, Linus O; Hothi, Parvinder; Basran, Jaswir; Ranaghan, Kara E; Mulholland, Adrian J; Leys, David; Scrutton, Nigel S

    2006-01-01

    It is now widely accepted that enzyme-catalysed C–H bond breakage occurs by quantum mechanical tunnelling. This paradigm shift in the conceptual framework for these reactions away from semi-classical transition state theory (TST, i.e. including zero-point energy, but with no tunnelling correction) has been driven over the recent years by experimental studies of the temperature dependence of kinetic isotope effects (KIEs) for these reactions in a range of enzymes, including the tryptophan tryptophylquinone-dependent enzymes such as methylamine dehydrogenase and aromatic amine dehydrogenase, and the flavoenzymes such as morphinone reductase and pentaerythritol tetranitrate reductase, which produced observations that are also inconsistent with the simple Bell-correction model of tunnelling. However, these data—especially, the strong temperature dependence of reaction rates and the variable temperature dependence of KIEs—are consistent with other tunnelling models (termed full tunnelling models), in which protein and/or substrate fluctuations generate a configuration compatible with tunnelling. These models accommodate substrate/protein (environment) fluctuations required to attain a configuration with degenerate nuclear quantum states and, when necessary, motion required to increase the probability of tunnelling in these states. Furthermore, tunnelling mechanisms in enzymes are supported by atomistic computational studies performed within the framework of modern TST, which incorporates quantum nuclear effects. PMID:16873125

  16. Rhodium-catalysed syn-carboamination of alkenes via a transient directing group.

    PubMed

    Piou, Tiffany; Rovis, Tomislav

    2015-11-01

    Alkenes are the most ubiquitous prochiral functional groups--those that can be converted from achiral to chiral in a single step--that are accessible to synthetic chemists. For this reason, difunctionalization reactions of alkenes (whereby two functional groups are added to the same double bond) are particularly important, as they can be used to produce highly complex molecular architectures. Stereoselective oxidation reactions, including dihydroxylation, aminohydroxylation and halogenation, are well established methods for functionalizing alkenes. However, the intermolecular incorporation of both carbon- and nitrogen-based functionalities stereoselectively across an alkene has not been reported. Here we describe the rhodium-catalysed carboamination of alkenes at the same (syn) face of a double bond, initiated by a carbon-hydrogen activation event that uses enoxyphthalimides as the source of both the carbon and the nitrogen functionalities. The reaction methodology allows for the intermolecular, stereospecific formation of one carbon-carbon and one carbon-nitrogen bond across an alkene, which is, to our knowledge, unprecedented. The reaction design involves the in situ generation of a bidentate directing group and the use of a new cyclopentadienyl ligand to control the reactivity of rhodium. The results provide a new way of synthesizing functionalized alkenes, and should lead to the convergent and stereoselective assembly of amine-containing acyclic molecules.

  17. Arginine demethylation is catalysed by a subset of JmjC histone lysine demethylases

    PubMed Central

    Walport, Louise J.; Hopkinson, Richard J.; Chowdhury, Rasheduzzaman; Schiller, Rachel; Ge, Wei; Kawamura, Akane; Schofield, Christopher J.

    2016-01-01

    While the oxygen-dependent reversal of lysine Nɛ-methylation is well established, the existence of bona fide Nω-methylarginine demethylases (RDMs) is controversial. Lysine demethylation, as catalysed by two families of lysine demethylases (the flavin-dependent KDM1 enzymes and the 2-oxoglutarate- and oxygen-dependent JmjC KDMs, respectively), proceeds via oxidation of the N-methyl group, resulting in the release of formaldehyde. Here we report detailed biochemical studies clearly demonstrating that, in purified form, a subset of JmjC KDMs can also act as RDMs, both on histone and non-histone fragments, resulting in formaldehyde release. RDM catalysis is studied using peptides of wild-type sequences known to be arginine-methylated and sequences in which the KDM's methylated target lysine is substituted for a methylated arginine. Notably, the preferred sequence requirements for KDM and RDM activity vary even with the same JmjC enzymes. The demonstration of RDM activity by isolated JmjC enzymes will stimulate efforts to detect biologically relevant RDM activity. PMID:27337104

  18. Extraction of copper from an oxidized (lateritic) ore using bacterially catalysed reductive dissolution.

    PubMed

    Nancucheo, Ivan; Grail, Barry M; Hilario, Felipe; du Plessis, Chris; Johnson, D Barrie

    2014-01-01

    An oxidized lateritic ore which contained 0.8 % (by weight) copper was bioleached in pH- and temperature-controlled stirred reactors under acidic reducing conditions using pure and mixed cultures of the acidophilic chemolithotrophic bacterium Acidithiobacillus ferrooxidans. Sulfur was provided as the electron donor for the bacteria, and ferric iron present in goethite (the major ferric iron mineral present in the ore) acted as electron acceptor. Significantly more copper was leached by bacterially catalysed reductive dissolution of the laterite than in aerobic cultures or in sterile anoxic reactors, with up to 78 % of the copper present in the ore being extracted. This included copper that was leached from acid-labile minerals (chiefly copper silicates) and that which was associated with ferric iron minerals in the lateritic ore. In the anaerobic bioreactors, soluble iron in the leach liquors was present as iron (II) and copper as copper (I), but both metals were rapidly oxidized (to iron (III) and copper (II)) when the reactors were aerated. The number of bacteria added to the reactors had a critical role in dictating the rate and yield of copper solubilised from the ore. This work has provided further evidence that reductive bioprocessing, a recently described approach for extracting base metals from oxidized deposits, has the potential to greatly extend the range of metal ores that can be biomined.

  19. Rhodium-catalysed asymmetric allylic arylation of racemic halides with arylboronic acids

    NASA Astrophysics Data System (ADS)

    Sidera, Mireia; Fletcher, Stephen P.

    2015-11-01

    Csp2-Csp2 cross-coupling reactions between arylboronic acid and aryl halides are widely used in both academia and industry and are strategically important in the development of new agrochemicals and pharmaceuticals. Csp2-Csp3 cross-coupling reactions have been developed, but enantioselective variations are rare and simply retaining the stereochemistry is a problem. Here we report a highly enantioselective Csp2-Csp3 bond-forming method that couples arylboronic acids to racemic allyl chlorides. Both enantiomers of a cyclic chloride are converted into a single enantiomer of product via a dynamic kinetic asymmetric transformation. This Rh-catalysed method uses readily available and inexpensive building blocks and is mild and broadly applicable. For electron-deficient, electron-rich or ortho-substituted boronic acids better results are obtained with racemic allyl bromides. Oxygen substitution in the allyl halide is tolerated and the products can be functionalized to provide diverse building blocks. The approach fills a significant gap in the methods for catalytic asymmetric synthesis.

  20. Fluorescent labelling of in situ hybridisation probes through the copper-catalysed azide-alkyne cycloaddition reaction.

    PubMed

    Hesse, Susann; Manetto, Antonio; Cassinelli, Valentina; Fuchs, Jörg; Ma, Lu; Raddaoui, Nada; Houben, Andreas

    2016-09-01

    In situ hybridisation is a powerful tool to investigate the genome and chromosome architecture. Nick translation (NT) is widely used to label DNA probes for fluorescence in situ hybridisation (FISH). However, NT is limited to the use of long double-stranded DNA and does not allow the labelling of single-stranded and short DNA, e.g. oligonucleotides. An alternative technique is the copper(I)-catalysed azide-alkyne cycloaddition (CuAAC), at which azide and alkyne functional groups react in a multistep process catalysed by copper(I) ions to give 1,4-distributed 1,2,3-triazoles at a high yield (also called 'click reaction'). We successfully applied this technique to label short single-stranded DNA probes as well as long PCR-derived double-stranded probes and tested them by FISH on plant chromosomes and nuclei. The hybridisation efficiency of differently labelled probes was compared to those obtained by conventional labelling techniques. We show that copper(I)-catalysed azide-alkyne cycloaddition-labelled probes are reliable tools to detect different types of repetitive sequences on chromosomes opening new promising routes for the detection of single copy gene. Moreover, a combination of FISH using such probes with other techniques, e.g. immunohistochemistry (IHC) and cell proliferation assays using 5-ethynyl-deoxyuridine, is herein shown to be easily feasible. PMID:27095480

  1. Unravelling RNA-substrate interactions in a ribozyme-catalysed reaction using fluorescent turn-on probes.

    PubMed

    Gaffarogullari, Ece Cazibe; Greulich, Peter; Kobitski, Andrei Yu; Nierth, Alexander; Nienhaus, G Ulrich; Jäschke, Andres

    2015-04-01

    The Diels-Alder reaction is one of the most important C-C bond-forming reactions in organic chemistry, and much effort has been devoted to controlling its enantio- and diastereoselectivity. The Diels-Alderase ribozyme (DAse) catalyses the reaction between anthracene dienes and maleimide dienophiles with multiple-turnover, stereoselectivity, and up to 1100-fold rate acceleration. Here, a new generation of anthracene-BODIPY-based fluorescent probes was developed to monitor catalysis by the DAse. The brightness of these probes increases up to 93-fold upon reaction with N-pentylmaleimide (NPM), making these useful tools for investigating the stereochemistry of the ribozyme-catalysed reaction. With these probes, we observed that the DAse catalyses the reaction with >91% de and >99% ee. The stereochemistry of the major product was determined unambiguously by rotating-frame nuclear Overhauser NMR spectroscopy (ROESY-NMR) and is in agreement with crystallographic structure information. The pronounced fluorescence change of the probes furthermore allowed a complete kinetic analysis, which revealed an ordered bi uni type reaction mechanism, with the dienophile binding first.

  2. Uncatalysed and catalysed soot combustion under NO{sub x} + O{sub 2}: Real diesel versus model soots

    SciTech Connect

    Atribak, I.; Bueno-Lopez, A.; Garcia-Garcia, A.

    2010-11-15

    In this work, the uncatalysed and catalysed combustion of two commercial carbon blacks and three diesel soot samples were analysed and related to the physico-chemical properties of these carbon materials. Model soot samples are less reactive than real soot samples, which can be attributed, mainly, to a lower proportion in heteroatoms and a higher graphitic order for the case of one of the carbon blacks. Among the diesel soot samples tested, the most relevant differences are the volatile matter/fixed carbon contents, which are directly related to the engine operating conditions (idle or loaded) and to the use of an oxidation catalyst or not in the exhaust. The soot collected after an oxidation catalyst (A-soot) is more reactive than the counterpart virgin soot obtained under the same engine operating modes but before the oxidation catalyst. The reactivity of the different soot samples follows the same trend under uncatalysed and catalysed combustion, the combustion profiles being always shifted towards lower temperatures for the catalysed reactions. The differences between the soot samples become less relevant in the presence of a catalyst. The ceria-zirconia catalysts tested are very effective not only to oxidise soot but also to combust the soluble organic fraction emitted at low temperatures. The most reactive soot (A-soot) exhibits a T{sub 50%} parameter of 450 C when using the most active catalyst. (author)

  3. Enzymatic synthesis of enantiopure alpha- and beta-amino acids by phenylalanine aminomutase-catalysed amination of cinnamic acid derivatives.

    PubMed

    Wu, Bian; Szymanski, Wiktor; Wietzes, Piet; de Wildeman, Stefaan; Poelarends, Gerrit J; Feringa, Ben L; Janssen, Dick B

    2009-01-26

    The phenylalanine aminomutase (PAM) from Taxus chinensis catalyses the conversion of alpha-phenylalanine to beta-phenylalanine, an important step in the biosynthesis of the N-benzoyl phenylisoserinoyl side-chain of the anticancer drug taxol. Mechanistic studies on PAM have suggested that (E)-cinnamic acid is an intermediate in the mutase reaction and that it can be released from the enzyme's active site. Here we describe a novel synthetic strategy that is based on the finding that ring-substituted (E)-cinnamic acids can serve as a substrate in PAM-catalysed ammonia addition reactions for the biocatalytic production of several important beta-amino acids. The enzyme has a broad substrate range and a high enantioselectivity with cinnamic acid derivatives; this allows the synthesis of several non-natural aromatic alpha- and beta-amino acids in excellent enantiomeric excess (ee >99 %). The internal 5-methylene-3,5-dihydroimidazol-4-one (MIO) cofactor is essential for the PAM-catalysed amination reactions. The regioselectivity of amination reactions was influenced by the nature of the ring substituent.

  4. An ecotoxicological study on tin- and bismuth-catalysed PDMS based coatings containing a surface-active polymer.

    PubMed

    Pretti, Carlo; Oliva, Matteo; Mennillo, Elvira; Barbaglia, Martina; Funel, Marco; Reddy Yasani, Bhaskar; Martinelli, Elisa; Galli, Giancarlo

    2013-12-01

    Novel films were prepared by condensation curing reaction of a poly(dimethyl siloxane) (PDMS) matrix with bismuth neodecanoate and dibutyltin diacetate catalysts. An ecotoxicological study was performed on the leachates of the coatings using the bacterium Vibrio fischeri, the unicellular alga Dunaliella tertiolecta, the crustacean Artemia salina and the fish Sparus aurata (larvae) as testing organisms. A copper-based self-polishing commercial paint was also tested as reference. The results showed that the tin-catalysed coatings and the copper paint were highly toxic against at least two of the four test organisms, whereas bismuth-catalysed coatings did not show any toxic effect. Moreover, the same biological assessment was also carried out on PDMS coatings containing a surface-active fluorinated polymer. The toxicity of the entire polymeric system resulted only from the tin catalyst used for the condensation curing reaction, as the bismuth catalysed coatings incorporating the surface-active polymer remained atoxic toward all the tested organisms. PMID:24125869

  5. View from east to west of PAR site storage building; ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    View from east to west of PAR site storage building; formerly PAR dispensary - Stanley R. Mickelsen Safeguard Complex, Storage Building, Across street from Family Housing Units 110 & 111, Nekoma, Cavalier County, ND

  6. View from west to east of PAR site resident engineer's ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    View from west to east of PAR site resident engineer's office building (REOB) - Stanley R. Mickelsen Safeguard Complex, Resident Engineers Office Building, Southeast of intersection of PAR Access Road & Fourth Avenue, Nekoma, Cavalier County, ND

  7. Conversion du methanol en ethanol par carbonylation suivie d'hydrogenolyse

    NASA Astrophysics Data System (ADS)

    Gaucher, Melissa

    Ce projet de maîtrise s'inscrit dans le cadre des nouvelles filières énergétiques renouvelables et s'effectue au sein de la Chaire de recherche industrielle sur l'éthanol cellulosique créée par trois partenaires industriels (Enerkem, CRB et Ethanol Greenfield) et le gouvernement du Québec en collaboration avec l'Université de Sherbrooke. La stratégie d'un des partenaires, Enerkem, est de convertir par gazéification des résidus de biomasse non homogène en Syngas, ce gaz est ensuite converti en méthanol puis en éthanol. L'objectif principal de ce projet est la conversion catalytique de l'acétate en alcool. Un catalyseur commercial, composé de cuivre et de chrome, a permis l'obtention des conversions de plus de 95 % et une sélectivité pour l'éthanol de plus de 50 % avec l'acétate de méthyle, de 99 % avec l'acétate d'éthyle et de 50 % avec l'acétate de butyle. Les conditions optimales trouvées impliquent une température de 215 °C, une pression de 350 psig, une vitesse spatiale de 1800 h -1 H2 STP et un ratio H2 : Acétate de 7. Un catalyseur alternatif, à base de cuivre et de zinc, a aussi été testé. L'objectif secondaire est la carbonylation du méthanol en acétate. Cette étape a été réalisée en phase gazeuse où des rendements très élevés, soit plus de 2000 kg d'acétate de méthyle par kg de métal précieux à l'heure (kg AM/ kg métal précieux/h), ont été obtenus. Les conditions d'opérations testées impliquent une température variant entre 200-240 °C, une pression entre 250-600 psig, des ratios McOH : CO de 1 à 2,5. Mots clés: Carbonylation, Éthanol, Hydrogénolyse, Catalyse hétérogène.

  8. A Combined Global and Local Approach to Elucidate Spatial Organization of the Mycobacterial ParB-parS Partition Assembly

    SciTech Connect

    B Chaudhuri; S Gupta; V Urban; M Chance; R DMello; L Smith; K Lyons; J Gee

    2011-12-31

    Combining diverse sets of data at global (size, shape) and local (residue) scales is an emerging trend for elucidating the organization and function of the cellular assemblies. We used such a strategy, combining data from X-ray and neutron scattering with H/D-contrast variation and X-ray footprinting with mass spectrometry, to elucidate the spatial organization of the ParB-parS assembly from Mycobacterium tuberculosis. The ParB-parS participates in plasmid and chromosome segregation and condensation in predivisional bacterial cells. ParB polymerizes around the parS centromere(s) to form a higher-order assembly that serves to recruit cyto-skeletal ParA ATPases and SMC proteins for chromosome segregation. A hybrid model of the ParB-parS was built by combining and correlating computational models with experiment-derived information about size, shape, position of the symmetry axis within the shape, internal topology, DNA-protein interface, exposed surface patches, and prior knowledge. This first view of the ParB-parS leads us to propose how ParB spread on the chromosome to form a larger assembly.

  9. A combined global and local approach to elucidate spatial organization of the Mycobacterial ParB-parS partition assembly.

    PubMed

    Chaudhuri, Barnali N; Gupta, Sayan; Urban, Volker S; Chance, Mark R; D'Mello, Rhijuta; Smith, Lauren; Lyons, Kelly; Gee, Jessica

    2011-03-22

    Combining diverse sets of data at global (size, shape) and local (residue) scales is an emerging trend for elucidating the organization and function of the cellular assemblies. We used such a strategy, combining data from X-ray and neutron scattering with H/D-contrast variation and X-ray footprinting with mass spectrometry, to elucidate the spatial organization of the ParB-parS assembly from Mycobacterium tuberculosis. The ParB-parS participates in plasmid and chromosome segregation and condensation in predivisional bacterial cells. ParB polymerizes around the parS centromere(s) to form a higher-order assembly that serves to recruit cyto-skeletal ParA ATPases and SMC proteins for chromosome segregation. A hybrid model of the ParB-parS was built by combining and correlating computational models with experiment-derived information about size, shape, position of the symmetry axis within the shape, internal topology, DNA-protein interface, exposed surface patches, and prior knowledge. This first view of the ParB-parS leads us to propose how ParB spread on the chromosome to form a larger assembly.

  10. A Combined Global and Local Approach to Elucidate Spatial Organization of the Mycobacterial ParB-parS Partition

    SciTech Connect

    Chaudhuri, Barnali; Gupta, Sayan; Urban, Volker S; Chance, Mark; D'Mello, Rhijuta; Smith, Lauren; Lyons, Kelly; Gee, Jessica

    2010-01-01

    Combining diverse sets of data at global (size, shape) and local (residue) scales is an emerging trend for elucidating the organization and function of the cellular assemblies. We used such a strategy, combining data from X-ray and neutron scattering with H/D-contrast variation and X-ray footprinting with mass spectrometry, to elucidate the spatial organization of the ParB-parS assembly from Mycobacterium tuberculosis. The ParB-parS participates in plasmid and chromosome segregation and condensation in predivisional bacterial cells. ParB polymerizes around the parS centromere(s) to form a higher-order assembly that serves to recruit cyto-skeletal ParA ATPases and SMC proteins for chromosome segregation. A hybrid model of the ParB-parS was built by combining and correlating computational models with experiment-derived information about size, shape, position of the symmetry axis within the shape, internal topology, DNA-protein interface, exposed surface patches, and prior knowledge. This first view of the ParB-parS leads us to propose how ParB spread on the chromosome to form a larger assembly.

  11. Host response biomarker in sepsis: suPAR detection.

    PubMed

    Giamarellos-Bourboulis, Evangelos J; Georgitsi, Marianna

    2015-01-01

    Recent studies of our group have shown that suPAR may complement APACHE II score for risk assessment in sepsis. suPAR may be measured in serum of patients by an enzyme immunosorbent assay developed by Virogates (suPARnostic™). Production of suPAR from circulating neutrophils and monocytes may be assessed after isolation of neutrophils and monocytes and ex vivo culture. This is followed by measurement of suPAR in culture supernatants.

  12. Advocating for malaria elimination - learning from the successes of other infectious disease elimination programmes.

    PubMed

    Whittaker, Maxine A; Dean, Angela J; Chancellor, Arna

    2014-01-01

    Malaria elimination is back on the agenda, but it remains challenging for countries to make the transition from effective control to elimination. Many other infectious diseases have been targeted by globally-coordinated elimination advocacy campaigns, and advocacy has been considered an essential component of the success of other disease elimination programmes. What can the malaria community learn from these successes? A review of infectious disease elimination programmes to identify successful elements of advocacy for disease elimination was undertaken. Key elements are: (i) a global elimination plan, supported by international health bodies; (ii) thorough costings and tools to support the business case; (iii) an approach that is positioned within a development framework; (iv) core elimination advocacy messages; (v) provision of advocacy tools for partners (vi) extensive and effective community engagement; and (vii) strong partnerships. These features provide insights into 'what works' in global elimination advocacy. Advocacy is a powerful tool to support the long-term political and financial commitment necessary for malaria elimination. The global malaria community needs to work together, to ensure that the early steps towards the end goal of malaria elimination are taken. PMID:24902848

  13. Advocating for malaria elimination - learning from the successes of other infectious disease elimination programmes.

    PubMed

    Whittaker, Maxine A; Dean, Angela J; Chancellor, Arna

    2014-06-05

    Malaria elimination is back on the agenda, but it remains challenging for countries to make the transition from effective control to elimination. Many other infectious diseases have been targeted by globally-coordinated elimination advocacy campaigns, and advocacy has been considered an essential component of the success of other disease elimination programmes. What can the malaria community learn from these successes? A review of infectious disease elimination programmes to identify successful elements of advocacy for disease elimination was undertaken. Key elements are: (i) a global elimination plan, supported by international health bodies; (ii) thorough costings and tools to support the business case; (iii) an approach that is positioned within a development framework; (iv) core elimination advocacy messages; (v) provision of advocacy tools for partners (vi) extensive and effective community engagement; and (vii) strong partnerships. These features provide insights into 'what works' in global elimination advocacy. Advocacy is a powerful tool to support the long-term political and financial commitment necessary for malaria elimination. The global malaria community needs to work together, to ensure that the early steps towards the end goal of malaria elimination are taken.

  14. Advocating for malaria elimination - learning from the successes of other infectious disease elimination programmes

    PubMed Central

    2014-01-01

    Malaria elimination is back on the agenda, but it remains challenging for countries to make the transition from effective control to elimination. Many other infectious diseases have been targeted by globally-coordinated elimination advocacy campaigns, and advocacy has been considered an essential component of the success of other disease elimination programmes. What can the malaria community learn from these successes? A review of infectious disease elimination programmes to identify successful elements of advocacy for disease elimination was undertaken. Key elements are: (i) a global elimination plan, supported by international health bodies; (ii) thorough costings and tools to support the business case; (iii) an approach that is positioned within a development framework; (iv) core elimination advocacy messages; (v) provision of advocacy tools for partners (vi) extensive and effective community engagement; and (vii) strong partnerships. These features provide insights into ‘what works’ in global elimination advocacy. Advocacy is a powerful tool to support the long-term political and financial commitment necessary for malaria elimination. The global malaria community needs to work together, to ensure that the early steps towards the end goal of malaria elimination are taken. PMID:24902848

  15. Unique slider bed eliminates problematic idler rollers

    SciTech Connect

    Not Available

    1988-01-01

    Solidur Plastic's impact slide bed is an innovative solution to problems with idler rollers. The unit provides increased conveyor efficiency and prolonged belt life. It also reduces costly downtime and maintenance needs by eliminating typical idler and conveyor belting problems.

  16. Why Should We Pivot in Gaussian Elimination?

    ERIC Educational Resources Information Center

    Rozema, Edward

    1988-01-01

    The article discusses the use of computers to teacher college level mathematics. In particular, the Gaussian elimination procedure for solving a system of n linear equations in n unknowns, using a computer, is examined. (PK)

  17. Intestinal elimination of ciprofloxacin in rabbits.

    PubMed Central

    Ramon, J; Dautrey, S; Farinoti, R; Carbon, C; Rubinstein, E

    1994-01-01

    The intestinal transepithelial elimination of ciprofloxacin was studied in a rabbit model. Jejunal, ileal, and cecal segments along with their intact blood vessels were isolated and perfused, and their contents were collected over a 120-min period following administration of a single parenteral dose of 27 mg of ciprofloxacin per kg of body weight. The intestinal elimination rates of ciprofloxacin were 0.126 +/- 0.084, 0.235 +/- 0.22, and 0.11 +/- 0.084 micrograms.min-1.cm-2 for the jejunal, ileal, and cecal segments, respectively. The calculated fractions of ciprofloxacin eliminated were 3.3 mg from the jejunum and 13.8 mg from the ileum, representing 19% of the administered dose. Additional amounts of 2.5 to 3.7 mg or 4.9 to 7.3% of the administered dose were eliminated from the cecum. Elimination was probably not due to a passive diffusion process but rather due to an active transepithelial transport. This intestinal elimination pattern of ciprofloxacin may explain the unusual activity of the fluoroquinolones in modifying the intestinal flora. PMID:8031042

  18. Proteinase-activated receptors (PARs) as targets for antiplatelet therapy.

    PubMed

    Cunningham, Margaret; McIntosh, Kathryn; Bushell, Trevor; Sloan, Graeme; Plevin, Robin

    2016-04-15

    Since the identification of the proteinase-activated receptor (PAR) family as mediators of serine protease activity in the 1990s, there has been tremendous progress in the elucidation of their pathophysiological roles. The development of drugs that target PARs has been the focus of many laboratories for the potential treatment of thrombosis, cancer and other inflammatory diseases. Understanding the mechanisms of PAR activation and G protein signalling pathways evoked in response to the growing list of endogenous proteases has yielded great insight into receptor regulation at the molecular level. This has led to the development of new selective modulators of PAR activity, particularly PAR1. The mixed success of targeting PARs has been best exemplified in the context of inhibiting PAR1 as a new antiplatelet therapy. The development of the competitive PAR1 antagonist, vorapaxar (Zontivity), has clearly shown the value in targeting PAR1 in acute coronary syndrome (ACS); however the severity of associated bleeding with this drug has limited its use in the clinic. Due to the efficacy of thrombin acting via PAR1, strategies to selectively inhibit specific PAR1-mediated G protein signalling pathways or to target the second thrombin platelet receptor, PAR4, are being devised. The rationale behind these alternative approaches is to bias downstream thrombin activity via PARs to allow for inhibition of pro-thrombotic pathways but maintain other pathways that may preserve haemostatic balance and improve bleeding profiles for widespread clinical use. This review summarizes the structural determinants that regulate PARs and the modulators of PAR activity developed to date.

  19. Les Brulures Chimiques Par Le Laurier Rose

    PubMed Central

    Bakkali, H.; Ababou, M.; Nassim Sabah, T.; Moussaoui, A.; Ennouhi, A.; Fouadi, F.Z.; Siah, S.; Ihrai, H.

    2010-01-01

    Summary Le laurier rose ou Nerium oleander est un arbuste qui pousse naturellement dans les régions méditerranéennes. Au Maroc on le trouve dans les lieux humides. Il est réputé par ses risques de toxicité systémique en cas d'empoisonnement à cause de la présence de deux alcaloïdes, surtout l'oléandrine. La littérature illustre des cas d'utilisation locale des feuilles de cette plante contre la gale, les hémorroïdes et les furoncles. Nous rapportons deux cas de brûlures chimiques par le laurier rose de gravité différente. Cela doit aboutir à une information élargie de la population, ainsi qu'une réglementation stricte de sa commercialisation. PMID:21991211

  20. Discovery of Octahydroindenes as PAR1 Antagonists

    PubMed Central

    2013-01-01

    Octahydroindene was identified as a novel scaffold for protease activated receptor 1 (PAR1) antagonists. Herein, the 2-position (C2) was explored for structure–activity relationship (SAR) studies. Compounds 14, 19, and 23b showed IC50 values of 1.3, 8.6, and 2.7 nM in a PAR1 radioligand binding assay, respectively, and their inhibitory activities on platelet activation were comparable to that of vorapaxar in a platelet rich plasma (PRP) aggregation assay. This series of compounds showed high potency and no significant cytotoxicity; however, the compounds were metabolically unstable in both human and rat liver microsomes. Current research efforts are focused on optimizing the compounds to improve metabolic stability and physicochemical properties as well as potency. PMID:24900604

  1. Combined DSEK and Transconjunctival Pars Plana Vitrectomy

    PubMed Central

    Sane, Mona; Shaikh, Naazli

    2016-01-01

    We report here three patients who underwent combined Descemet's stripping with endothelial keratoplasty and transconjunctival pars plana vitrectomy for bullous keratopathy and posterior segment pathology. A surgical technique and case histories are described. Anatomic and visual outcomes of combined Descemet's stripping with endothelial keratoplasty and vitrectomy were excellent. Our experience provides technical guidelines and limitations. The combined minimally invasive techniques allow for rapid anatomical recovery and return of function and visual acuity in a single sitting. PMID:27413563

  2. Par Pond refill water quality sampling

    SciTech Connect

    Koch, J.W. II; Martin, F.D.; Westbury, H.M.

    1996-08-01

    This study was designed to document anoxia and its cause in the event that the anoxia caused a fish kill. However, no fish kill was observed during this study, and dissolved oxygen and nutrient concentrations generally remained within the range expected for southeastern reservoirs. Par Pond water quality monitoring will continue during the second summer after refill as the aquatic macrophytes become reestablished and nutrients in the sediments are released to the water column.

  3. The mechanism of the reaction catalysed by adenosine triphosphate–creatine phosphotransferase

    PubMed Central

    Morrison, J. F.; James, Elizabeth

    1965-01-01

    1. The forward and reverse reactions catalysed by ATP–creatine phosphotransferase have been studied kinetically at pH8·0 in the presence and absence of products, under conditions in which the free Mg2+ concentration was maintained constant at 1mm. Thus at fixed pH the reaction may be considered as being bireactant and expressed as:MgATP2−+creatine0⇌MgADP−+phosphocreatine2−2. The initial-velocity pattern in the absence of products and the product-inhibition pattern have been determined. These are consistent with a random mechanism in which all steps are in rapid equilibrium except that concerned with the interconversion of the central ternary complexes, and in which two dead-end complexes (enzyme–MgADP–creatine and enzyme–MgATP–phosphocreatine) are formed. The results are in accord with previous suggestions that the enzyme possesses distinct sites for the combination of the nucleotide and guanidino substrates. 3. Values have been determined for the Michaelis and dissociation constants involved in the combination of each substrate with various enzyme forms. Although these values cannot be regarded as absolute, they appear to indicate that the presence of one substrate on the enzyme enhances the combination of the second substrate. In addition, it would seem that in the formation of the enzyme–MgADP–creatine complex the concentration of one reactant does not affect the combination of the other. This contrasts with the formation of the enzyme–MgATP–phosphocreatine complex, where each reactant hinders the combination of the other. PMID:16749122

  4. Kinetics of acyl transfer reactions in organic media catalysed by Candida antarctica lipase B.

    PubMed

    Martinelle, M; Hult, K

    1995-09-01

    The acyl transfer reactions catalysed by Candida antartica lipase B in organic media followed a bi-bi ping-pong mechanism, with competitive substrate inhibition by the alcohols used as acyl acceptors. The effect of organic solvents on Vm and Km was investigated. The Vm values in acetonitrile was 40-50% of those in heptane. High Km values in acetonitrile compared to those in heptane could partly be explained by an increased solvation of the substrates in acetonitrile. Substrate solvation caused a 10-fold change in substrate specificity, defined as (Vm/Km)ethyl octanoate/(Vm/Km)octanoic acid, going from heptane to acetonitrile. Deacylation was the rate determining step for the acyl transfer in heptane with vinyl- and ethyl octanoate as acyl donors and (R)-2-octanol as acyl acceptor. With 1-octanol, a rate determining deacylation step in heptane was indicated using the same acyl donors. Using 1-octanol as acceptor in heptane, S-ethyl thiooctanoate had a 25- to 30-fold lower Vm/Km value and vinyl octanoate a 4-fold higher Vm/Km value than that for ethyl octanoate. The difference showed to be a Km effect for vinyl octanoate and mainly a Km effect for S-ethyl thiooctanoate. The Vm values of the esterification of octanoic acid with different alcohols was 10-30-times lower than those for the corresponding transesterification of ethyl octanoate. The low activity could be explained by a low pH around the enzyme caused by the acid or a withdrawing of active enzyme by nonproductive binding by the acid. PMID:7669809

  5. Cryptococcus neoformans laccase catalyses melanin synthesis from both D- and L-DOPA.

    PubMed

    Eisenman, Helene C; Mues, Mascha; Weber, Sarah E; Frases, Susana; Chaskes, Stuart; Gerfen, Gary; Casadevall, Arturo

    2007-12-01

    The human fungal pathogen Cryptococcus neoformans produces melanin in the presence of various substrates, including the L enantiomer of 3,4-dihydroxyphenylalanine (DOPA). The enzyme laccase catalyses the formation of melanin by oxidizing L-DOPA, initiating a series of presumably spontaneous reactions that ultimately leads to the polymerization of the pigment in the yeast cell wall. There, melanin protects the cell from a multitude of environmental and host assaults. Thus, the ability of C. neoformans to produce pigments from a variety of available substrates is likely to confer a survival advantage. A number of C. neoformans isolates of different serotypes produced pigments from D-DOPA, the stereoisomer of L-DOPA. Acid-resistant particles were isolated from pigmented C. neoformans cells grown in the presence of D-DOPA. Biophysical characterization showed the particles had a stably detectable free-radical signal by EPR, and negative zeta potential, similar to L-DOPA-derived particles. No major differences were found between L- and D-DOPA ghosts in terms of binding to anti-melanin antibodies, or in overall architecture when imaged by electron microscopy. C. neoformans cells utilized L- and D-DOPA at a similar rate. Overall, our results indicate that C. neoformans shows little stereoselectivity for utilizing DOPA in melanin synthesis. The ability of C. neoformans to use both L and D enantiomers for melanization implies that this organism has access to a greater potential pool of substrates for melanin synthesis, and this could potentially be exploited in the design of therapeutic inhibitors of laccase.

  6. Kinetics of acyl transfer reactions in organic media catalysed by Candida antarctica lipase B.

    PubMed

    Martinelle, M; Hult, K

    1995-09-01

    The acyl transfer reactions catalysed by Candida antartica lipase B in organic media followed a bi-bi ping-pong mechanism, with competitive substrate inhibition by the alcohols used as acyl acceptors. The effect of organic solvents on Vm and Km was investigated. The Vm values in acetonitrile was 40-50% of those in heptane. High Km values in acetonitrile compared to those in heptane could partly be explained by an increased solvation of the substrates in acetonitrile. Substrate solvation caused a 10-fold change in substrate specificity, defined as (Vm/Km)ethyl octanoate/(Vm/Km)octanoic acid, going from heptane to acetonitrile. Deacylation was the rate determining step for the acyl transfer in heptane with vinyl- and ethyl octanoate as acyl donors and (R)-2-octanol as acyl acceptor. With 1-octanol, a rate determining deacylation step in heptane was indicated using the same acyl donors. Using 1-octanol as acceptor in heptane, S-ethyl thiooctanoate had a 25- to 30-fold lower Vm/Km value and vinyl octanoate a 4-fold higher Vm/Km value than that for ethyl octanoate. The difference showed to be a Km effect for vinyl octanoate and mainly a Km effect for S-ethyl thiooctanoate. The Vm values of the esterification of octanoic acid with different alcohols was 10-30-times lower than those for the corresponding transesterification of ethyl octanoate. The low activity could be explained by a low pH around the enzyme caused by the acid or a withdrawing of active enzyme by nonproductive binding by the acid.

  7. Defective Cytochrome P450-Catalysed Drug Metabolism in Niemann-Pick Type C Disease.

    PubMed

    Nicoli, Elena-Raluca; Al Eisa, Nada; Cluzeau, Celine V M; Wassif, Christopher A; Gray, James; Burkert, Kathryn R; Smith, David A; Morris, Lauren; Cologna, Stephanie M; Peer, Cody J; Sissung, Tristan M; Uscatu, Constantin-Daniel; Figg, William D; Pavan, William J; Vite, Charles H; Porter, Forbes D; Platt, Frances M

    2016-01-01

    Niemann-Pick type C (NPC) disease is a neurodegenerative lysosomal storage disease caused by mutations in either the NPC1 or NPC2 gene. NPC is characterised by storage of multiple lipids in the late endosomal/lysosomal compartment, resulting in cellular and organ system dysfunction. The underlying molecular mechanisms that lead to the range of clinical presentations in NPC are not fully understood. While evaluating potential small molecule therapies in Npc1-/- mice, we observed a consistent pattern of toxicity associated with drugs metabolised by the cytochrome P450 system, suggesting a potential drug metabolism defect in NPC1 disease. Investigation of the P450 system in the context of NPC1 dysfunction revealed significant changes in the gene expression of many P450 associated genes across the full lifespan of Npc1-/- mice, decreased activity of cytochrome P450 reductase, and a global decrease of multiple cytochrome P450 catalysed dealkylation reactions. In vivo drug metabolism studies using a prototypic P450 metabolised drug, midazolam, confirmed dysfunction in drug clearance in the Npc1-/- mouse. Expression of the Phase II enzyme uridinediphosphate-glucuronosyltransferase (UGT) was also significantly reduced in Npc1-/- mice. Interestingly, reduced activity within the P450 system was also observed in heterozygous Npc1+/- mice. The reduced activity of P450 enzymes may be the result of bile acid deficiency/imbalance in Npc1-/- mice, as bile acid treatment significantly rescued P450 enzyme activity in Npc1-/- mice and has the potential to be an adjunctive therapy for NPC disease patients. The dysfunction in the cytochrome P450 system were recapitulated in the NPC1 feline model. Additionally, we present the first evidence that there are alterations in the P450 system in NPC1 patients. PMID:27019000

  8. Defective Cytochrome P450-Catalysed Drug Metabolism in Niemann-Pick Type C Disease

    PubMed Central

    Wassif, Christopher A.; Gray, James; Burkert, Kathryn R.; Smith, David A.; Morris, Lauren; Cologna, Stephanie M.; Peer, Cody J.; Sissung, Tristan M.; Uscatu, Constantin-Daniel; Figg, William D.; Pavan, William J.; Vite, Charles H.; Porter, Forbes D.; Platt, Frances M.

    2016-01-01

    Niemann-Pick type C (NPC) disease is a neurodegenerative lysosomal storage disease caused by mutations in either the NPC1 or NPC2 gene. NPC is characterised by storage of multiple lipids in the late endosomal/lysosomal compartment, resulting in cellular and organ system dysfunction. The underlying molecular mechanisms that lead to the range of clinical presentations in NPC are not fully understood. While evaluating potential small molecule therapies in Npc1-/- mice, we observed a consistent pattern of toxicity associated with drugs metabolised by the cytochrome P450 system, suggesting a potential drug metabolism defect in NPC1 disease. Investigation of the P450 system in the context of NPC1 dysfunction revealed significant changes in the gene expression of many P450 associated genes across the full lifespan of Npc1-/- mice, decreased activity of cytochrome P450 reductase, and a global decrease of multiple cytochrome P450 catalysed dealkylation reactions. In vivo drug metabolism studies using a prototypic P450 metabolised drug, midazolam, confirmed dysfunction in drug clearance in the Npc1-/- mouse. Expression of the Phase II enzyme uridinediphosphate-glucuronosyltransferase (UGT) was also significantly reduced in Npc1-/- mice. Interestingly, reduced activity within the P450 system was also observed in heterozygous Npc1+/- mice. The reduced activity of P450 enzymes may be the result of bile acid deficiency/imbalance in Npc1-/- mice, as bile acid treatment significantly rescued P450 enzyme activity in Npc1-/- mice and has the potential to be an adjunctive therapy for NPC disease patients. The dysfunction in the cytochrome P450 system were recapitulated in the NPC1 feline model. Additionally, we present the first evidence that there are alterations in the P450 system in NPC1 patients. PMID:27019000

  9. Structure-activity relationships for chemical and glutathione S-transferase-catalysed glutathione conjugation reactions of a series of 2-substituted 1-chloro-4-nitrobenzenes.

    PubMed Central

    Van der Aar, E M; Bouwman, T; Commandeur, J N; Vermeulen, N P

    1996-01-01

    Glutathione S-transferases (GSTs) constitute an important class of phase II (de)toxifying enzymes, catalysing the conjugation of glutathione (GSH) with electrophilic compounds. In the present study, Km, kcat and kcat/Km values for the rat GST 1-1-, 3-3-, 4-4- and 7-7-catalysed conjugation reactions between GSH and a series of 10 different 2-substituted 1-chloro-4-nitrobenzenes, and the second-order rate constants (ks) of the corresponding base-catalysed reactions, were correlated with nine classical physicochemical parameters (electronic, steric and lipophilic) of the substituents and with 16 computer-calculated molecular parameters of the substrates and of the corresponding Meisenheimer complexes with MeS- as a model nucleophile for GS- (charge distributions and several energy values), giving structure-activity relationships. On the basis of an identical dependence of the base-catalysed as well as the GST 1-1- and GST 7-7-catalysed reactions on electronic parameters (among others, Hammett substituent constant sigma p and charge on p-nitro substituents), and the finding that the corresponding reactions catalysed by GSTs 3-3 and 4-4 depend to a significantly lesser extent on these parameters, it was concluded that the Mu-class GST isoenzymes have a rate-determining transition state in the conjugation reaction between 2-substituted 1-chloro-4-nitrobenzenes and GSH which is different from that of the other two GSTs. Several alternative rate-limiting transition states for GST 3-3 and 4-4 are discussed. Furthermore, based on the obtained structure-activity relationships, it was possible to predict the kcat/Km values of the four GST isoenzymes and the ks of the base-catalysed GSH conjugation of 1-chloro-4-nitrobenzene. PMID:8973562

  10. Aminophobanes: hydrolytic stability, tautomerism and application in Cr-catalysed ethene oligomerisation.

    PubMed

    Haddow, Mairi F; Jaltai, Judit; Hanton, Martin; Pringle, Paul G; Rush, Laura E; Sparkes, Hazel A; Woodall, Christopher H

    2016-02-01

    9-Amino-9-phosphabicyclo[3.3.1]nonanes, (PhobPNHR'; R = Me or (i)Pr) are readily prepared by aminolysis of PhobPCl and are significantly less susceptible to hydrolysis than the acyclic analogues Cy2PNHR'. Treatment of Cy2PNHMe with Cy2PCl readily gave Cy2PNMePCy2. By contrast, treatment of PhobPCl with PhobPNHMe in the presence of Et3N does not afford PhobPNMePPhob but instead the salt [PhobP(= NMeH)PPhob]Cl is formed which, upon addition of [PtCl2(NC(t)Bu)2] gives the zwitterionic complex [PtCl3(PhobP(= NMeH)PPhob)]. The neutral PhobP(= NMe)PPhob is accessible from PhobNMeLi and is converted to the chelate [PdCl2(PhobPNMePPhob)] by addition of [PdCl2(cod)]. The anomalous preference of the PhobP group for the formation of PPN products is discussed. The unsymmetrical diphos ligands PhobPNMePAr2 (Ar = Ph, o-Tol) are prepared, converted to [Cr(CO)4(PhobPNMePAr2)] and shown to form Cr-catalysts for ethene oligomerisation, producing a pattern of higher alkenes that corresponds to a Schulz-Flory distribution overlaid on selective tri/tetramerisation. PMID:26779965

  11. Body elimination attitude family resemblance in Kuwait.

    PubMed

    Al-Fayez, Ghenaim; Awadalla, Abdelwahid; Arikawa, Hiroko; Templer, Donald I; Hutton, Shane

    2009-12-01

    The purpose of the present study was to determine the family resemblance of attitude toward body elimination in Kuwaiti participants. This study was conceptualized in the context of the theories of moral development, importance of cleanliness in the Muslim religion, cross-cultural differences in personal hygiene practices, previous research reporting an association between family attitudes and body elimination attitude, and health implications. The 24-item Likert-type format Body Elimination Attitude Scale-Revised was administered to 277 Kuwaiti high school students and 437 of their parents. Females scored higher, indicating greater disgust, than the males. Moreover, sons' body elimination attitude correlated more strongly with fathers' attitude (r = .85) than with that of the mothers (r = .64). Daughters' attitude was similarly associated with the fathers' (r = .89) and the mothers' attitude (r = .86). The high correlations were discussed within the context of Kuwait having a collectivistic culture with authoritarian parenting style. The higher adolescent correlations, and in particular the boys' correlation with fathers than with mothers, was explained in terms of the more dominant role of the Muslim father in the family. Public health and future research implications were suggested. A theoretical formulation was advanced in which "ideal" body elimination attitude is relative rather than absolute, and is a function of one's life circumstances, one's occupation, one's culture and subculture, and the society that one lives in.

  12. Martian Atmospheric Pressure Static Charge Elimination Tool

    NASA Technical Reports Server (NTRS)

    Johansen, Michael R.

    2014-01-01

    A Martian pressure static charge elimination tool is currently in development in the Electrostatics and Surface Physics Laboratory (ESPL) at NASA's Kennedy Space Center. In standard Earth atmosphere conditions, static charge can be neutralized from an insulating surface using air ionizers. These air ionizers generate ions through corona breakdown. The Martian atmosphere is 7 Torr of mostly carbon dioxide, which makes it inherently difficult to use similar methods as those used for standard atmosphere static elimination tools. An initial prototype has been developed to show feasibility of static charge elimination at low pressure, using corona discharge. A needle point and thin wire loop are used as the corona generating electrodes. A photo of the test apparatus is shown below. Positive and negative high voltage pulses are sent to the needle point. This creates positive and negative ions that can be used for static charge neutralization. In a preliminary test, a floating metal plate was charged to approximately 600 volts under Martian atmospheric conditions. The static elimination tool was enabled and the voltage on the metal plate dropped rapidly to -100 volts. This test data is displayed below. Optimization is necessary to improve the electrostatic balance of the static elimination tool.

  13. Eliminating discipline problems by strengthening academic performance.

    PubMed

    Ayllon, T; Roberts, M D

    1974-01-01

    Behavior modification procedures have typically been used to eliminate discipline problems in the classroom through reinforcement of nondisruptive behavior. This report demonstrates an alternative approach whereby discipline problems are eliminated by reinforcing relevant academic skills. Five fifth-grade boys, identified by their teacher as discipline problems, were observed. The teacher conducted 15-min performance sessions in her reading class during which written academic performance and disruptive behavior were recorded. These measures indicated that the boys' average level of disruption was 34%, while their reading performance was below 50%. When systematic token reinforcement was applied to reading performance only, the rate of disruption fell drastically, and reading performance increased. When the reinforcement procedure was withdrawn, disruption again rose, and reading performance declined. The reinstatement of reinforcement doubled reading performance and eliminated disruption. PMID:4465374

  14. Eliminating discipline problems by strengthening academic performance.

    PubMed

    Ayllon, T; Roberts, M D

    1974-01-01

    Behavior modification procedures have typically been used to eliminate discipline problems in the classroom through reinforcement of nondisruptive behavior. This report demonstrates an alternative approach whereby discipline problems are eliminated by reinforcing relevant academic skills. Five fifth-grade boys, identified by their teacher as discipline problems, were observed. The teacher conducted 15-min performance sessions in her reading class during which written academic performance and disruptive behavior were recorded. These measures indicated that the boys' average level of disruption was 34%, while their reading performance was below 50%. When systematic token reinforcement was applied to reading performance only, the rate of disruption fell drastically, and reading performance increased. When the reinforcement procedure was withdrawn, disruption again rose, and reading performance declined. The reinstatement of reinforcement doubled reading performance and eliminated disruption.

  15. Regulator of G protein signaling 2 (RGS2) and RGS4 form distinct G protein-dependent complexes with protease activated-receptor 1 (PAR1) in live cells.

    PubMed

    Ghil, Sungho; McCoy, Kelly L; Hepler, John R

    2014-01-01

    Protease-activated receptor 1 (PAR1) is a G-protein coupled receptor (GPCR) that is activated by natural proteases to regulate many physiological actions. We previously reported that PAR1 couples to Gi, Gq and G12 to activate linked signaling pathways. Regulators of G protein signaling (RGS) proteins serve as GTPase activating proteins to inhibit GPCR/G protein signaling. Some RGS proteins interact directly with certain GPCRs to modulate their signals, though cellular mechanisms dictating selective RGS/GPCR coupling are poorly understood. Here, using bioluminescence resonance energy transfer (BRET), we tested whether RGS2 and RGS4 bind to PAR1 in live COS-7 cells to regulate PAR1/Gα-mediated signaling. We report that PAR1 selectively interacts with either RGS2 or RGS4 in a G protein-dependent manner. Very little BRET activity is observed between PAR1-Venus (PAR1-Ven) and either RGS2-Luciferase (RGS2-Luc) or RGS4-Luc in the absence of Gα. However, in the presence of specific Gα subunits, BRET activity was markedly enhanced between PAR1-RGS2 by Gαq/11, and PAR1-RGS4 by Gαo, but not by other Gα subunits. Gαq/11-YFP/RGS2-Luc BRET activity is promoted by PAR1 and is markedly enhanced by agonist (TFLLR) stimulation. However, PAR1-Ven/RGS-Luc BRET activity was blocked by a PAR1 mutant (R205A) that eliminates PAR1-Gq/11 coupling. The purified intracellular third loop of PAR1 binds directly to purified His-RGS2 or His-RGS4. In cells, RGS2 and RGS4 inhibited PAR1/Gα-mediated calcium and MAPK/ERK signaling, respectively, but not RhoA signaling. Our findings indicate that RGS2 and RGS4 interact directly with PAR1 in Gα-dependent manner to modulate PAR1/Gα-mediated signaling, and highlight a cellular mechanism for selective GPCR/G protein/RGS coupling.

  16. Has Wild Poliovirus Been Eliminated from Nigeria?

    PubMed

    Famulare, Michael

    2015-01-01

    Wild poliovirus type 3 (WPV3) has not been seen anywhere since the last case of WPV3-associated paralysis in Nigeria in November 2012. At the time of writing, the most recent case of wild poliovirus type 1 (WPV1) in Nigeria occurred in July 2014, and WPV1 has not been seen in Africa since a case in Somalia in August 2014. No cases associated with circulating vaccine-derived type 2 poliovirus (cVDPV2) have been detected in Nigeria since November 2014. Has WPV1 been eliminated from Africa? Has WPV3 been eradicated globally? Has Nigeria interrupted cVDPV2 transmission? These questions are difficult because polio surveillance is based on paralysis and paralysis only occurs in a small fraction of infections. This report provides estimates for the probabilities of poliovirus elimination in Nigeria given available data as of March 31, 2015. It is based on a model of disease transmission that is built from historical polio incidence rates and is designed to represent the uncertainties in transmission dynamics and poliovirus detection that are fundamental to interpreting long time periods without cases. The model estimates that, as of March 31, 2015, the probability of WPV1 elimination in Nigeria is 84%, and that if WPV1 has not been eliminated, a new case will be detected with 99% probability by the end of 2015. The probability of WPV3 elimination (and thus global eradication) is > 99%. However, it is unlikely that the ongoing transmission of cVDPV2 has been interrupted; the probability of cVDPV2 elimination rises to 83% if no new cases are detected by April 2016. PMID:26317401

  17. Pd-catalysed direct arylation polymerisation for synthesis of low-bandgap conjugated polymers and photovoltaic performance.

    PubMed

    Chang, Shu-Wei; Waters, Huw; Kettle, Jeff; Kuo, Zi-Rui; Li, Chun-Han; Yu, Chin-Yang; Horie, Masaki

    2012-11-23

    Low-bandgap conjugated copolymers based on a donor-acceptor structure have been synthesised via palladium-complex catalysed direct arylation polymerisation. Initially, we report the optimisation of the synthesis of poly(cyclopentadithiophene-alt-benzothiadiazole) (PCPDTBT) formed between cyclopentadithiophene and dibromobenzothiadiazole units. The polymerisation condition has been optimised, which affords high-molecular-weight polymers of up to M(n) = 70 k using N-methylpyrrolidone as a solvent. The polymers are used to fabricate organic photovoltaic devices and the best performing PCPDTBT device exhibits a moderate improvement over devices fabricated using the related polymer via Suzuki coupling. Similar polymerisation conditions have also been applied for other monomer units.

  18. Noise elimination algorithm for modal analysis

    SciTech Connect

    Bao, X. X.; Li, C. L.; Xiong, C. B.

    2015-07-27

    Modal analysis is an ongoing interdisciplinary physical issue. Modal parameters estimation is applied to determine the dynamic characteristics of structures under vibration excitation. Modal analysis is more challenging for the measured vibration response signals are contaminated with noise. This study develops a mathematical algorithm of structured low rank approximation combined with the complex exponential method to estimate the modal parameters. Physical experiments using a steel cantilever beam with ten accelerometers mounted, excited by an impulse load, demonstrate that this method can significantly eliminate noise from measured signals and accurately identify the modal frequencies and damping ratios. This study provides a fundamental mechanism of noise elimination using structured low rank approximation in physical fields.

  19. Recognizing, Confronting, and Eliminating Workplace Bullying.

    PubMed

    Berry, Peggy Ann; Gillespie, Gordon L; Fisher, Bonnie S; Gormley, Denise K

    2016-07-01

    Workplace bullying (WPB) behaviors negatively affect nurse productivity, satisfaction, and retention, and hinder safe patient care. The purpose of this article is to define WPB, differentiate between incivility and WPB, and recommend actions to prevent WPB behaviors. Informed occupational and environmental health nurses and nurse leaders must recognize, confront, and eliminate WPB in their facilities and organizations. Recognizing, confronting, and eliminating WPB behaviors in health care is a crucial first step toward sustained improvements in patient care quality and the health and safety of health care employees. PMID:27053288

  20. Leprosy New Case Detection Trends and the Future Effect of Preventive Interventions in Pará State, Brazil: A Modelling Study

    PubMed Central

    de Matos, Haroldo José; Blok, David J.; de Vlas, Sake J.; Richardus, Jan Hendrik

    2016-01-01

    Background Leprosy remains a public health problem in Brazil. Although the overall number of new cases is declining, there are still areas with a high disease burden, such as Pará State in the north of the country. We aim to predict future trends in new case detection rate (NCDR) and explore the potential impact of contact tracing and chemoprophylaxis on NCDR in Pará State. Methods We used SIMCOLEP, an existing individual-based model for the transmission and control of M. leprae, in a population structured by households. The model was quantified to simulate the population and observed NCDR of leprosy in Pará State for the period 1990 to 2014. The baseline scenario was the current control program, consisting of multidrug therapy, passive case detection, and active case detection from 2003 onwards. Future projections of the NCDR were made until 2050 given the continuation of the current control program (i.e. baseline). We further investigated the potential impact of two scenarios for future control of leprosy: 1) discontinuation of contact tracing; and 2) continuation of current control in combination with chemoprophylaxis. Both scenarios started in 2015 and were projected until 2050. Results The modelled NCDR in Pará State after 2014 shows a continuous downward trend, reaching the official elimination target of 10 cases per 100,000 population by 2030. The cessation of systematic contact tracing would not result in a higher NCDR in the long run. Systematic contact tracing in combination with chemoprophylaxis for contacts would reduce the NCDR by 40% and bring attainment of the elimination target two years forward to 2028. Conclusion The NCDR of leprosy continues to decrease in Pará State. Elimination of leprosy as a public health problem could possibly be achieved around 2030, if the current control program is maintained. Providing chemoprophylaxis would decrease the NCDR further and would bring elimination forward by two years. PMID:26938738

  1. Alkaline-Earth-Catalysed Cross-Dehydrocoupling of Amines and Hydrosilanes: Reactivity Trends, Scope and Mechanism.

    PubMed

    Bellini, Clément; Dorcet, Vincent; Carpentier, Jean-François; Tobisch, Sven; Sarazin, Yann

    2016-03-18

    Alkaline-earth (Ae=Ca, Sr, Ba) complexes are shown to catalyse the chemoselective cross-dehydrocoupling (CDC) of amines and hydrosilanes. Key trends were delineated in the benchmark couplings of Ph3 SiH with pyrrolidine or tBuNH2 . Ae{E(SiMe3)2}2 ⋅(THF)x (E=N, CH; x=2-3) are more efficient than {N^N}Ae{E(SiMe3)2}⋅(THF)n (E=N, CH; n=1-2) complexes (where {N^N}(-) ={ArN(o-C6H4)C(H)=NAr}(-) with Ar=2,6-iPr2 -C6H3) bearing an iminoanilide ligand, and alkyl precatalysts are better than amido analogues. Turnover frequencies (TOFs) increase in the order Ca30 products) includes diamines and di(hydrosilane)s. Kinetic analysis of the Ba-promoted CDC of pyrrolidine and Ph3SiH shows that 1) the kinetic law is rate=k[Ba](1) [amine](0) [hydrosilane](1), 2) electron-withdrawing p-substituents on the arylhydrosilane improve the reaction rate and 3) a maximal kinetic isotopic effect (kSiH/kSiD =4.7) is seen for Ph3SiX (X=H, D). DFT calculations identified the prevailing mechanism; instead of an inaccessible σ-bond-breaking metathesis pathway, the CDC appears to follow a stepwise reaction path with N-Si bond-forming nucleophilic attack of the catalytically competent Ba pyrrolide onto the incoming silane, followed by rate limiting hydrogen-atom transfer to barium. The participation of a Ba silyl species is prevented energetically. The reactivity trend Ca

  2. Alkaline-Earth-Catalysed Cross-Dehydrocoupling of Amines and Hydrosilanes: Reactivity Trends, Scope and Mechanism.

    PubMed

    Bellini, Clément; Dorcet, Vincent; Carpentier, Jean-François; Tobisch, Sven; Sarazin, Yann

    2016-03-18

    Alkaline-earth (Ae=Ca, Sr, Ba) complexes are shown to catalyse the chemoselective cross-dehydrocoupling (CDC) of amines and hydrosilanes. Key trends were delineated in the benchmark couplings of Ph3 SiH with pyrrolidine or tBuNH2 . Ae{E(SiMe3)2}2 ⋅(THF)x (E=N, CH; x=2-3) are more efficient than {N^N}Ae{E(SiMe3)2}⋅(THF)n (E=N, CH; n=1-2) complexes (where {N^N}(-) ={ArN(o-C6H4)C(H)=NAr}(-) with Ar=2,6-iPr2 -C6H3) bearing an iminoanilide ligand, and alkyl precatalysts are better than amido analogues. Turnover frequencies (TOFs) increase in the order Ca30 products) includes diamines and di(hydrosilane)s. Kinetic analysis of the Ba-promoted CDC of pyrrolidine and Ph3SiH shows that 1) the kinetic law is rate=k[Ba](1) [amine](0) [hydrosilane](1), 2) electron-withdrawing p-substituents on the arylhydrosilane improve the reaction rate and 3) a maximal kinetic isotopic effect (kSiH/kSiD =4.7) is seen for Ph3SiX (X=H, D). DFT calculations identified the prevailing mechanism; instead of an inaccessible σ-bond-breaking metathesis pathway, the CDC appears to follow a stepwise reaction path with N-Si bond-forming nucleophilic attack of the catalytically competent Ba pyrrolide onto the incoming silane, followed by rate limiting hydrogen-atom transfer to barium. The participation of a Ba silyl species is prevented energetically. The reactivity trend Ca

  3. Modelisation par elements finis du muscle strie

    NASA Astrophysics Data System (ADS)

    Leonard, Mathieu

    Ce present projet de recherche a permis. de creer un modele par elements finis du muscle strie humain dans le but d'etudier les mecanismes engendrant les lesions musculaires traumatiques. Ce modele constitue une plate-forme numerique capable de discerner l'influence des proprietes mecaniques des fascias et de la cellule musculaire sur le comportement dynamique du muscle lors d'une contraction excentrique, notamment le module de Young et le module de cisaillement de la couche de tissu conjonctif, l'orientation des fibres de collagene de cette membrane et le coefficient de poisson du muscle. La caracterisation experimentale in vitro de ces parametres pour des vitesses de deformation elevees a partir de muscles stries humains actifs est essentielle pour l'etude de lesions musculaires traumatiques. Le modele numerique developpe est capable de modeliser la contraction musculaire comme une transition de phase de la cellule musculaire par un changement de raideur et de volume a l'aide des lois de comportement de materiau predefinies dans le logiciel LS-DYNA (v971, Livermore Software Technology Corporation, Livermore, CA, USA). Le present projet de recherche introduit donc un phenomene physiologique qui pourrait expliquer des blessures musculaires courantes (crampes, courbatures, claquages, etc.), mais aussi des maladies ou desordres touchant le tissu conjonctif comme les collagenoses et la dystrophie musculaire. La predominance de blessures musculaires lors de contractions excentriques est egalement exposee. Le modele developpe dans ce projet de recherche met ainsi a l'avant-scene le concept de transition de phase ouvrant la porte au developpement de nouvelles technologies pour l'activation musculaire chez les personnes atteintes de paraplegie ou de muscles artificiels compacts pour l'elaboration de protheses ou d'exosquelettes. Mots-cles Muscle strie, lesion musculaire, fascia, contraction excentrique, modele par elements finis, transition de phase

  4. Eliminating Sexism from Children's Theatre Productions.

    ERIC Educational Resources Information Center

    Johnston, Kaarin S.

    To help reduce sexism in children's theatre productions, directors should make a conscious effort to eliminate negative patterns from scripts. They should give attention to the roles of the characters, since female characters are often relegated to the roles of waiting for a male, a supportive parent or sister, or a passive admirer of a male.…

  5. Gram-Schmidt Orthogonalization by Gauss Elimination.

    ERIC Educational Resources Information Center

    Pursell, Lyle; Trimble, S. Y.

    1991-01-01

    Described is the hand-calculation method for the orthogonalization of a given set of vectors through the integration of Gaussian elimination with existing algorithms. Although not numerically preferable, this method adds increased precision as well as organization to the solution process. (JJK)

  6. Efficient genotype elimination via adaptive allele consolidation.

    PubMed

    De Francesco, Nicoletta; Lettieri, Giuseppe; Martini, Luca

    2012-01-01

    We propose the technique of Adaptive Allele Consolidation, that greatly improves the performance of the Lange-Goradia algorithm for genotype elimination in pedigrees, while still producing equivalent output. Genotype elimination consists in removing from a pedigree those genotypes that are impossible according to the Mendelian law of inheritance. This is used to find errors in genetic data and is useful as a preprocessing step in other analyses (such as linkage analysis or haplotype imputation). The problem of genotype elimination is intrinsically combinatorial, and Allele Consolidation is an existing technique where several alleles are replaced by a single “lumped” allele in order to reduce the number of combinations of genotypes that have to be considered, possibly at the expense of precision. In existing Allele Consolidation techniques, alleles are lumped once and for all before performing genotype elimination. The idea of Adaptive Allele Consolidation is to dynamically change the set of alleles that are lumped together during the execution of the Lange-Goradia algorithm, so that both high performance and precision are achieved. We have implemented the technique in a tool called Celer and evaluated it on a large set of scenarios, with good results.

  7. Tackling Imported Malaria: An Elimination Endgame

    PubMed Central

    Sturrock, Hugh J. W.; Roberts, Kathryn W.; Wegbreit, Jennifer; Ohrt, Colin; Gosling, Roly D.

    2015-01-01

    As countries move toward malaria elimination, imported infections become increasingly significant as they often represent the majority of cases, can sustain transmission, cause resurgences, and lead to mortality. Here we review and critique current methods to prevent malaria importation in countries pursuing elimination and explore methods applied in other transmission settings and to other diseases that could be transferred to support malaria elimination. To improve intervention targeting we need a better understanding of the characteristics of populations importing infections and their patterns of migration, improved methods to reliably classify infections as imported or acquired locally, and ensure early and accurate diagnosis. The potential for onward transmission in the most receptive and vulnerable locations can be predicted through high-resolution risk mapping that can help malaria elimination or prevention of reintroduction programs target resources. Cross border and regional initiatives can be highly effective when based on an understanding of human and parasite movement. Ultimately, determining the optimal combinations of approaches to address malaria importation will require an evaluation of their impact, cost effectiveness, and operational feasibility. PMID:26013369

  8. Lymphatic filariasis: Treatment, control and elimination.

    PubMed

    Ottesen, Eric A

    2006-01-01

    Lymphatic filariasis (LF) is a disease not just treatable or controllable; it is a disease that can be eliminated. Indeed, LF is currently the target of a major global initiative to do just that; a few visionaries of the past 50 years did hypothesize that LF elimination was feasible. However, for most of the scientific and global health communities, the elimination of such a broadly disseminated, mosquito-borne disease has seemed highly unlikely. During the past decade, however, both the treatment strategies and the control strategies for LF have undergone profound paradigm shifts-all because of a rapid increase in knowledge and understanding of LF that derived directly from a series of remarkable achievements by the scientific and medical research communities. As a result, a public health dimension with a focus on affected populations, now supplements the earlier, predominantly patient-oriented clinical approach to LF. The early uncertainties, then the essential steps leading to this change in outlook are outlined below, followed by descriptions of the new strategy for LF elimination, the Global Programme created to attain this goal and the successes achieved to date.

  9. Eliminating Barriers to Dual Enrollment in Oklahoma

    ERIC Educational Resources Information Center

    Roach, Rick; Gamez Vargas, Juanita; David, Kevin M.

    2015-01-01

    Policy, financial, and transportation barriers have limited participation in dual enrollment for marginalized (low-socioeconomic, first-generation, and ethnic minority) students in Oklahoma. This chapter presents a collaborative effort by education and community leaders that has successfully eliminated these barriers and increased the number of…

  10. Taking Centrioles to the elimination round

    PubMed Central

    Schoborg, Todd; Rusan, Nasser M.

    2016-01-01

    Two recent papers published in The Journal of Cell Biology (Borrego-Pinto et al., 2016) and Science ((Borrego-Pinto et al., 2016; Pimenta-Marques et al., 2016) have begun to shed light on the mechanism of centriole elimination during female oogenesis, highlighting a protective role for Polo kinase and the pericentriolar material. PMID:27404354

  11. Eliminating Problems Caused by Multicollinearity: A Warning.

    ERIC Educational Resources Information Center

    Kennedy, Peter E.

    1982-01-01

    Explains why an econometric practice introduced by J.C. Soper cannot eliminate the problems caused by multicollinearity. The author suggests that it can be a useful technique in that it forces researchers to pay more attention to the specifications of their models. (AM)

  12. Dispensing system eliminates torsion in deployed hoses

    NASA Technical Reports Server (NTRS)

    1965-01-01

    Dispensing system uses a rotating drum, transfer arm, and stationary drum to deploy, reel in, and store an attached hose. This system which eliminates torsion and minimizes strain and wear of flexible hoses, is used for handling flexible cables that have one end permanently attached to an outlet or connector.

  13. Rotational fluid coupling eliminates hose entanglements

    NASA Technical Reports Server (NTRS)

    Aubol, P. B.

    1966-01-01

    Rotational fluid coupling mechanism circulates a temperature controlled fluid between a stationary heat exchanger and a coolant plate on a rotating platform. The mechanism consists of two concentric cylinders containing one or more flexible tubes which are controlled and positioned in such a way that it eliminates tubing entanglement.

  14. Taking Centrioles to the Elimination Round.

    PubMed

    Schoborg, Todd A; Rusan, Nasser M

    2016-07-11

    Two recent papers published in The Journal of Cell Biology (Borrego-Pinto et al., 2016) and Science (Pimenta-Marques et al., 2016) have begun to shed light on the mechanism of centriole elimination during female oogenesis, highlighting a protective role for Polo kinase and the pericentriolar material. PMID:27404354

  15. Promoting Relationships and Eliminating Violence in Canada

    ERIC Educational Resources Information Center

    Pepler, Debra; Craig, Wendy

    2011-01-01

    The Promoting Relationships and Eliminating Violence Network (PREVNet) involves Canadian researchers and national organizations working to promote healthy relationships and prevent bullying. In this paper, we provide the rationale for establishing PREVNet, a description of the work of the network, and an assessment of the success of PREVNet.…

  16. Trefoil factor 3 (TFF3) from human breast milk activates PAR-2 receptors, of the intestinal epithelial cells HT-29, regulating cytokines and defensins.

    PubMed

    Barrera, G J; Tortolero, G Sanchez

    2016-01-01

    Trefoil factors are effector molecules in gastrointestinal tract physiology. Each one improves healing of the gastrointestinal tract. Trefoil factors may be grouped into three classes: the gastric peptides (TFF1), spasmolytic peptide (TFF2) and intestinal trefoil factor (TFF3). Significant amounts of TFF3 are present in human breast milk. Previously, we have reported that trefoil factor 3 isolated from human breast milk produces down regulation of cytokines and promotes human beta defensins expression in intestinal epithelial cells. This study aimed to determine the molecular mechanism involved. Here we showed that the presence of TFF3 strongly correlated with protease activated receptors 2 (PAR-2) activation in human intestinal cells. Intracellular calcium ((Ca2+)i)mobilization was induced by the treatment with: 1) TFF3, 2) synthetic PAR-2 agonist peptide. The co-treatment with a synthetic PAR-2 antagonist peptide and TFF3 eliminates the latter's effect. Additionally, we demonstrated the existence of interactions among TFF3 and PAR-2 receptors through far Western blot and co-precipitation. Finally, down regulation of PAR-2 by siRNA resulted in a decrease of TFF3 induced intracellular (Ca2+)i mobilization, cytokine regulation and defensins expression. These findings suggest that TFF3 activates intestinal cells through PAR-2 (Fig. 4, Ref. 19). PMID:27546365

  17. Endemicity response timelines for Plasmodium falciparum elimination

    PubMed Central

    Smith, David L; Hay, Simon I

    2009-01-01

    Background The scaling up of malaria control and renewed calls for malaria eradication have raised interest in defining timelines for changes in malaria endemicity. Methods The epidemiological theory for the decline in the Plasmodium falciparum parasite rate (PfPR, the prevalence of infection) following intervention was critically reviewed and where necessary extended to consider superinfection, heterogeneous biting, and aging infections. Timelines for malaria control and elimination under different levels of intervention were then established using a wide range of candidate mathematical models. Analysis focused on the timelines from baseline to 1% and from 1% through the final stages of elimination. Results The Ross-Macdonald model, which ignores superinfection, was used for planning during the Global Malaria Eradication Programme (GMEP). In models that consider superinfection, PfPR takes two to three years longer to reach 1% starting from a hyperendemic baseline, consistent with one of the few large-scale malaria control trials conducted in an African population with hyperendemic malaria. The time to elimination depends fundamentally upon the extent to which malaria transmission is interrupted and the size of the human population modelled. When the PfPR drops below 1%, almost all models predict similar and proportional declines in PfPR in consecutive years from 1% through to elimination and that the waiting time to reduce PfPR from 10% to 1% and from 1% to 0.1% are approximately equal, but the decay rate can increase over time if infections senesce. Conclusion The theory described herein provides simple "rules of thumb" and likely time horizons for the impact of interventions for control and elimination. Starting from a hyperendemic baseline, the GMEP planning timelines, which were based on the Ross-Macdonald model with completely interrupted transmission, were inappropriate for setting endemicity timelines and they represent the most optimistic scenario for

  18. A Conserved Mode of Protein Recognition and Binding in a ParD−ParE Toxin−Antitoxin Complex

    SciTech Connect

    Dalton, Kevin M.; Crosson, Sean

    2010-05-06

    Toxin-antitoxin (TA) systems form a ubiquitous class of prokaryotic proteins with functional roles in plasmid inheritance, environmental stress response, and cell development. ParDE family TA systems are broadly conserved on plasmids and bacterial chromosomes and have been well characterized as genetic elements that promote stable plasmid inheritance. We present a crystal structure of a chromosomally encoded ParD-ParE complex from Caulobacter crescentus at 2.6 {angstrom} resolution. This TA system forms an {alpha}{sub 2}{beta}{sub 2} heterotetramer in the crystal and in solution. The toxin-antitoxin binding interface reveals extensive polar and hydrophobic contacts of ParD antitoxin helices with a conserved recognition and binding groove on the ParE toxin. A cross-species comparison of this complex structure with related toxin structures identified an antitoxin recognition and binding subdomain that is conserved between distantly related members of the RelE/ParE toxin superfamily despite a low level of overall primary sequence identity. We further demonstrate that ParD antitoxin is dimeric, stably folded, and largely helical when not bound to ParE toxin. Thus, the paradigmatic model in which antitoxin undergoes a disorder-to-order transition upon toxin binding does not apply to this chromosomal ParD-ParE TA system.

  19. Protease-activated receptor 1 (PAR1) signalling desensitization is counteracted via PAR4 signalling in human platelets.

    PubMed

    Fälker, Knut; Haglund, Linda; Gunnarsson, Peter; Nylander, Martina; Lindahl, Tomas L; Grenegård, Magnus

    2011-06-01

    PARs (protease-activated receptors) 1 and 4 belong to the family of G-protein-coupled receptors which induce both G(α12/13) and G(αq) signalling. By applying the specific PAR1- and PAR4-activating hexapeptides, SFLLRN and AYPGKF respectively, we found that aggregation of isolated human platelets mediated via PAR1, but not via PAR4, is abolished upon homologous receptor activation in a concentration- and time-dependent fashion. This effect was not due to receptor internalization, but to a decrease in Ca²⁺ mobilization, PKC (protein kinase C) signalling and α-granule secretion, as well as to a complete lack of dense granule secretion. Interestingly, subthreshold PAR4 activation rapidly abrogated PAR1 signalling desensitization by differentially reconstituting these affected signalling events and functional responses, which was sufficient to re-establish aggregation. The lack of ADP release and P2Y₁₂ receptor-induced G(αi) signalling accounted for the loss of the aggregation response, as mimicking G(αi/z) signalling with 2-MeS-ADP (2-methylthioadenosine-5'-O-diphosphate) or epinephrine (adrenaline) could substitute for intermediate PAR4 activation. Finally, we found that the re-sensitization of PAR1 signalling-induced aggregation via PAR4 relied on PKC-mediated release of both ADP from dense granules and fibrinogen from α-granules. The present study elucidates further differences in human platelet PAR signalling regulation and provides evidence for a cross-talk in which PAR4 signalling counteracts mechanisms involved in PAR1 signalling down-regulation. PMID:21391917

  20. Apoptosis and Tumor Resistance Conferred by Par-4

    PubMed Central

    Zhao, Yanming; Rangnekar, Vivek M.

    2009-01-01

    Par-4 is a tumor suppressor protein with a pro-apoptotic function. Epigenetic silencing of Par-4 is seen in diverse tumors, and Par-4 knockout mice develop spontaneous tumors in various tissues. Endogenous Par-4 is essential for sensitization of cells to diverse apoptotic stimuli, whereas ectopic expression of Par-4 can selectively induce apoptosis in cancer cells. The cancer-specific pro-apoptotic action of Par-4 resides in its centrally located SAC domain. This chapter reviews a novel mouse model with ubiquitous expression of the SAC domain. These SAC transgenic mice display normal development and life span, and, most importantly, are resistant to spontaneous, as well as oncogene-induced, autochthonous tumors. The tumor resistant phenotype and undetectable toxicity of SAC in vivo suggests the SAC domain possesses tremendous therapeutic potential. PMID:18836307

  1. The thiostrepton A tryptophan methyltransferase TsrM catalyses a cob(II)alamin-dependent methyl transfer reaction

    PubMed Central

    Benjdia, Alhosna; Pierre, Stéphane; Gherasim, Carmen; Guillot, Alain; Carmona, Manon; Amara, Patricia; Banerjee, Ruma; Berteau, Olivier

    2015-01-01

    Ribosomally synthesized and post-translationally modified peptides (RiPPs) are a novel class of natural products including several antibiotics and bacterial toxins. In countless RiPP biosynthetic pathways, cobalamin-dependent radical SAM (B12/rSAM) enzymes play a pivotal role. In the biosynthetic pathway of the antibiotic and anti-cancer agent thiostrepton A, TsrM, a B12/rSAM enzyme, catalyses the transfer of a methyl group to an electrophilic carbon atom of tryptophan. Here we show that methylcob(III)alamin is the probable physiological enzyme cofactor, and cob(II)alamin rather than cob(I)alamin is a key reaction intermediate. Furthermore, we establish that TsrM and a triple-alanine mutant alkylate cob(II)alamin efficiently leading to the synthesis of MeCbl. Exploiting TsrM substrate ambiguity, we demonstrate that TsrM does not catalyse substrate H-atom abstraction like most radical SAM enzymes. Based on these data, we propose an unprecedented radical-based C-methylation mechanism, which further expands the chemical versatility of rSAM enzymes. PMID:26456915

  2. A novel glucuronosyltransferase has an unprecedented ability to catalyse continuous two-step glucuronosylation of glycyrrhetinic acid to yield glycyrrhizin.

    PubMed

    Xu, Guojie; Cai, Wei; Gao, Wei; Liu, Chunsheng

    2016-10-01

    Glycyrrhizin is an important bioactive compound that is used clinically to treat chronic hepatitis and is also used as a sweetener world-wide. However, the key UDP-dependent glucuronosyltransferases (UGATs) involved in the biosynthesis of glycyrrhizin remain unknown. To discover unknown UGATs, we fully annotated potential UGATs from Glycyrrhiza uralensis using deep transcriptome sequencing. The catalytic functions of candidate UGATs were determined by an in vitro enzyme assay. Systematically screening 434 potential UGATs, we unexpectedly found one unique GuUGAT that was able to catalyse the glucuronosylation of glycyrrhetinic acid to directly yield glycyrrhizin via continuous two-step glucuronosylation. Expression analysis further confirmed the key role of GuUGAT in the biosynthesis of glycyrrhizin. Site-directed mutagenesis revealed that Gln-352 may be important for the initial step of glucuronosylation, and His-22, Trp-370, Glu-375 and Gln-392 may be important residues for the second step of glucuronosylation. Notably, the ability of GuUGAT to catalyse a continuous two-step glucuronosylation reaction was determined to be unprecedented among known glycosyltransferases of bioactive plant natural products. Our findings increase the understanding of traditional glycosyltransferases and pave the way for the complete biosynthesis of glycyrrhizin. PMID:27252088

  3. Chemical synthesis and papain-catalysed hydrolysis of N-alpha-benzyloxycarbonyl-L-lysine p-nitroanilide.

    PubMed Central

    Mackenzie, N E; Malthouse, J P; Scott, A I

    1985-01-01

    The chemical synthesis of N-alpha-benzyloxycarbonyl-L-lysine p-nitroanilide (Z-Lys-pNA) is described in detail. The pH-dependence of the catalytic parameters kcat,' Km and kcat./Km for the papain-catalysed hydrolysis of Z-Lys-pNA are determined. kcat. and Km are pH-independent between pH 5 and pH 7.42, but the pH-dependence of kcat./Km is bell-shaped, decreasing at high and low pH values with pKa values of 7.97 and 4.40 respectively. The catalytic parameters and their pH-dependence are shown to be similar to those reported for other anilide substrates and it is concluded that the Km value of 0.01 mM previously reported [Angelides & Fink (1979) Biochemistry 18, 2355-2369] is incorrect. The possibility of accumulating a tetrahedral intermediate during the papain-catalysed hydrolysis of Z-Lys-pNA is discussed. PMID:3922354

  4. The formation of high-purity isocyanurate through proazaphosphatrane-catalysed isocyanate cyclo-trimerisation: computational insights.

    PubMed

    Gibb, Jack N; Goodman, Jonathan M

    2013-01-01

    Polyurethane foams are widely used materials and control of their physical properties is a significant challenge. Management of cyclo-trimerisation during the polymerisation process is vital when tailoring the mechanical properties of the foam. Proazaphosphatranes are known to efficiently catalyse the cyclo-trimerisation of organic isocyanates, giving high purity isocyanurate with little uretdione by-product. The mechanism of this catalysis was previously unknown, although some zwitterionic intermediates have been identified spectroscopically. We have investigated a nucleophilic-catalysis reaction pathway involving sequential addition of methyl isocyanate to activated zwitterionic intermediates using density functional theory calculations. Evidence for significant transannulation by the proazaphosphatrane nitrogen was found for all intermediates, offering stabilisation of the phosphonium cation. Steric crowding at the proazaphosphatrane nucleophilic phosphorus gives rise to a preference for direct isocyanurate formation rather than via the uretdione, in sharp contrast to the uncatalysed system which has been found to preferentially proceed via the kinetic uretdione product. The investigations suggest the mechanism of proazaphosphatrane catalysed cyclo-oligomerisation does not proceed via the uretdione product, and hence why little of this impurity is observed experimentally.

  5. The sulphoxidation of thioanisole catalysed by lactoperoxidase and Coprinus cinereus peroxidase: evidence for an oxygen-rebound mechanism.

    PubMed

    Tuynman, A; Vink, M K; Dekker, H L; Schoemaker, H E; Wever, R

    1998-12-01

    Using both stopped-flow and conventional spectroscopy, the oxygenation of methyl phenyl sulphide by both lactoperoxidase (LPO) and Coprinus cinereus peroxidase (CiP) was monitored. Controlled continuous addition of H2O2 during turnover and monitoring the presence of native enzymes, compounds I, II and III, led to formation of the sulphoxide in high yield and enantioselectivity. Under those conditions, LPO catalysed the formation of (R) methyl phenyl sulphoxide with a yield of 85% and an enantiomeric excess (e.e.) of 80%. CiP catalysed the formation of (S) methyl phenyl sulphoxide with a yield of 84% and an e.e. of 73%. The enantioselective performance was markedly influenced by the purity of the enzymes used. Presence of compound III during turnover led to rapid inactivation of the peroxidases and, therefore, to both a lower yield of the sulphoxides and a lower enantioselectivity. Stopped-flow kinetic data show that, for both LPO and CiP, the transition of compound I to compound II depends on the concentration of the methyl phenyl sulphide, suggesting an oxygen-rebound mechanism. In line with this mechanism, a methyl phenyl sulphide radical cation was detected by EPR during turnover for LPO.

  6. Bifunctional CYP81AA proteins catalyse identical hydroxylations but alternative regioselective phenol couplings in plant xanthone biosynthesis

    PubMed Central

    El-Awaad, Islam; Bocola, Marco; Beuerle, Till; Liu, Benye; Beerhues, Ludger

    2016-01-01

    Xanthones are natural products present in plants and microorganisms. In plants, their biosynthesis starts with regioselective cyclization of 2,3′,4,6-tetrahydroxybenzophenone to either 1,3,5- or 1,3,7-trihydroxyxanthones, catalysed by cytochrome P450 (CYP) enzymes. Here we isolate and express CYP81AA-coding sequences from Hypericum calycinum and H. perforatum in yeast. Microsomes catalyse two consecutive reactions, that is, 3′-hydroxylation of 2,4,6-trihydroxybenzophenone and C–O phenol coupling of the resulting 2,3′,4,6-tetrahydroxybenzophenone. Relative to the inserted 3′-hydroxyl, the orthologues Hc/HpCYP81AA1 cyclize via the para position to form 1,3,7-trihydroxyxanthone, whereas the paralogue HpCYP81AA2 directs cyclization to the ortho position, yielding the isomeric 1,3,5-trihydroxyxanthone. Homology modelling and reciprocal mutagenesis reveal the impact of S375, L378 and A483 on controlling the regioselectivity of HpCYP81AA2, which is converted into HpCYP81AA1 by sextuple mutation. However, the reciprocal mutations in HpCYP81AA1 barely affect its regiospecificity. Product docking rationalizes the alternative C–O phenol coupling reactions. Our results help understand the machinery of bifunctional CYPs. PMID:27145837

  7. A novel glucuronosyltransferase has an unprecedented ability to catalyse continuous two-step glucuronosylation of glycyrrhetinic acid to yield glycyrrhizin.

    PubMed

    Xu, Guojie; Cai, Wei; Gao, Wei; Liu, Chunsheng

    2016-10-01

    Glycyrrhizin is an important bioactive compound that is used clinically to treat chronic hepatitis and is also used as a sweetener world-wide. However, the key UDP-dependent glucuronosyltransferases (UGATs) involved in the biosynthesis of glycyrrhizin remain unknown. To discover unknown UGATs, we fully annotated potential UGATs from Glycyrrhiza uralensis using deep transcriptome sequencing. The catalytic functions of candidate UGATs were determined by an in vitro enzyme assay. Systematically screening 434 potential UGATs, we unexpectedly found one unique GuUGAT that was able to catalyse the glucuronosylation of glycyrrhetinic acid to directly yield glycyrrhizin via continuous two-step glucuronosylation. Expression analysis further confirmed the key role of GuUGAT in the biosynthesis of glycyrrhizin. Site-directed mutagenesis revealed that Gln-352 may be important for the initial step of glucuronosylation, and His-22, Trp-370, Glu-375 and Gln-392 may be important residues for the second step of glucuronosylation. Notably, the ability of GuUGAT to catalyse a continuous two-step glucuronosylation reaction was determined to be unprecedented among known glycosyltransferases of bioactive plant natural products. Our findings increase the understanding of traditional glycosyltransferases and pave the way for the complete biosynthesis of glycyrrhizin.

  8. Silver-catalysed azide–alkyne cycloaddition (AgAAC): assessing the mechanism by density functional theory calculations

    PubMed Central

    Chandrasekhar, K.; Killi, Sunil Kumar; Pramanik, Sumit Kumar; Uttam, Pal; Sen, Sudeshna; Maiti, Nakul Chandra

    2016-01-01

    ‘Click reactions’ are the copper catalysed dipolar cycloaddition reaction of azides and alkynes to incorporate nitrogens into a cyclic hydrocarbon scaffold forming a triazole ring. Owing to its efficiency and versatility, this reaction and the products, triazole-containing heterocycles, have immense importance in medicinal chemistry. Copper is the only known catalyst to carry out this reaction, the mechanism of which remains unclear. We report here that the ‘click reactions’ can also be catalysed by silver halides in non-aqueous medium. It constitutes an alternative to the well-known CuAAC click reaction. The yield of the reaction varies on the type of counter ion present in the silver salt. This reaction exhibits significant features, such as high regioselectivity, mild reaction conditions, easy availability of substrates and reasonably good yields. In this communication, the findings of a new catalyst along with the effect of solvent and counter ions will help to decipher the still obscure mechanism of this important reaction. PMID:27703683

  9. Reversed reactivity of anilines with alkynes in the rhodium-catalysed C–H activation/carbonylation tandem

    PubMed Central

    Midya, Siba P.; Sahoo, Manoj K.; Landge, Vinod G.; Rajamohanan, P. R.; Balaraman, Ekambaram

    2015-01-01

    Development of multicatalytic approach consisting of two or more mechanistically distinct catalytic steps using a single-site catalyst for rapid and straightforward access of structurally complex molecules under eco-benign conditions has significance in contemporary science. We have developed herein a rhodium-catalysed C–H activation strategy which uses an unprotected anilines and an electron-deficient alkynes to C–C bonded products as a potential intermediate in contrast to the archetypical C–N bonded products with high levels of regioselectivity. This is followed by carbonylation of C–H bond activated intermediate and subsequent annulation into quinolines has been described. This rhodium-catalysed auto-tandem reaction operates under mild, environmentally benign conditions using water as the solvent and CO surrogates as the carbonyl source with the concomitant generation of hydrogen gas. The strategy may facilitate the development of new synthetic protocols for the efficient and sustainable production of chemicals in an atom-economic way from simple, abundant starting materials. PMID:26486182

  10. A new model for estimating boreal forest fPAR

    NASA Astrophysics Data System (ADS)

    Majasalmi, Titta; Rautiainen, Miina; Stenberg, Pauline

    2014-05-01

    Life on Earth is continuously sustained by the extraterrestrial flux of photosynthetically active radiation (PAR, 400-700 nm) from the sun. This flux is converted to biomass by chloroplasts in green vegetation. Thus, the fraction of absorbed PAR (fPAR) is a key parameter used in carbon balance studies, and is listed as one of the Essential Climate Variables (ECV). Temporal courses of fPAR for boreal forests are difficult to measure, because of the complex 3D structures. Thus, they are most often estimated based on models which quantify the dependency of absorbed radiation on canopy structure. In this study, we adapted a physically-based canopy radiation model into a fPAR model, and compared modeled and measured fPAR in structurally different boreal forest stands. The model is based on the spectral invariants theory, and uses leaf area index (LAI), canopy gap fractions and spectra of foliage and understory as input data. The model differs from previously developed more detailed fPAR models in that the complex 3D structure of coniferous forests is described using an aggregated canopy parameter - photon recollision probability p. The strength of the model is that all model inputs are measurable or available through other simple models. First, the model was validated with measurements of instantaneous fPAR obtained with the TRAC instrument in nine Scots pine, Norway spruce and Silver birch stands in a boreal forest in southern Finland. Good agreement was found between modeled and measured fPAR. Next, we applied the model to predict temporal courses of fPAR using data on incoming radiation from a nearby flux tower and sky irradiance models. Application of the model to simulate diurnal and seasonal values of fPAR indicated that the ratio of direct-to-total incident radiation and leaf area index are the key factors behind the magnitude and variation of stand-level fPAR values.

  11. Experimental and theoretical study of the mechanism of hydrolysis of substituted phenyl hexanoates catalysed by globin in the presence of surfactant.

    PubMed

    Ercan, Selami; Arslan, Nevin; Kocakaya, Safak Ozhan; Pirinccioglu, Necmettin; Williams, Andrew

    2014-03-01

    The bimolecular rate constants for the globin- and alkali-catalysed hydrolysis of substituted phenyl hexanoates in the absence and presence of cetyltrimethylammonium bromide (CTAB) obey Brønsted equations with β(lg) = -0.53 (globin-catalysed), -0.68 (globin-catalysed in CTAB), -0.34 (in water) and -0.74 (in CTAB), respectively. The slopes indicate that the microsolvation environments associated with the transition states of the catalysed reactions are different from those that occur in aqueous medium. The slope (-0.74) for the reaction in CTAB implies that it proceeds in a less polar medium. The larger β(lg) value (-0.53) obtained for the globin-catalysed reaction compared to that for the uncatalysed one may be attributed to either the less polar microenvironments of the transition states or the involvement of one of the imidazole groups as a nucleophile. The results from a study of the effect of pH on the reactivity provide evidence for the latter assumption. All of the ligands were docked into the hydrophobic pocket of the protein, and the resulting docking scores ranged from -30.76 to -23.61 kcal mol⁻¹. Molecular dynamic simulations and MM-PBSA/GBSA calculations performed for the complexes gave insight into the binding modes of globin to the esters, which are consistent with experimental results. The calculations yielded comparable free energies of binding to the experimental ones for 4-nitrophenyl and 4-chloro-2-nitrophenyl hexanoates. In conclusion, information obtained from the linear free-energy relationship is still very useful for elucidating the mechanisms of organic reactions, including enzyme-catalysed reactions. This approach is further supported by the utilization of computational tools.

  12. 2. HI PAR (ACQUISITION RADAR) TOWER AND ENLISTED MEN (EM) ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    2. HI PAR (ACQUISITION RADAR) TOWER AND ENLISTED MEN (EM) BARRACKS WITH RADAR ATTACHED. - Nike Hercules Missile Battery Summit Site, Battery Control Administration & Barracks Building, Anchorage, Anchorage, AK

  13. 1,4-Cyclohexadienes--easy access to a versatile building block via transition-metal-catalysed Diels-Alder reactions.

    PubMed

    Hilt, Gerhard

    2014-06-01

    1,4-Cyclohexadiene derivatives are easily accessed via transition-metal cycloadditions of 1,3-dienes with alkynes. The mild reaction conditions of several transition-metal-catalysed reactions allows the incorporation of various functional groups to access functionalised 1,4-cyclohexadienes. The control of the regiochemistry in the intermolecular cobalt-catalysed Diels-Alder reaction is realised utilising different ligand designs. The functionalised 1,4-cyclohexadiene derivatives are valuable building blocks in follow-up transformations. Finally, the oxidation of the 1,4-cyclohexadienes can be accomplished under mild conditions to generate the corresponding arene derivatives.

  14. Hydrogen generation from alcohols (α-hydroxy carboxylic acids) and alcohol-ammonia coupling in aqueous media catalysed by water-soluble bipyridine-Cp*Ir (Rh or Os) catalyst: a computational mechanism insight

    NASA Astrophysics Data System (ADS)

    Zhang, Dan-Dan; Chen, Xian-Kai; Liu, Hui-Ling; Huang, Xu-Ri

    2015-06-01

    Density functional theory (DFT) calculations were performed to elucidate the mechanism of the dehydrogenative oxidation of various primary alcohols (or α-hydroxy carboxylic acids) and the dehydrogenative coupling of alcohols with ammonia catalysed by the same water-soluble Cp*Ir complex bearing a 2-pyridonate-based ligand (A-Ir). Another two new catalysts A-Rh and A-Os are computationally designed for the dehydrogenative oxidation of alcohols. The plausible pathway for alcohol dehydrogenation includes three steps: alcohol oxidation to aldehyde (step I); the generation of dihydrogen in the metal coordination sphere (step II); and the liberation of dihydrogen accompanied with the regeneration of active catalyst A (step III). Among them, the step I follows bifunctional concerted double hydrogen transfer mechanism rather than the β-H elimination. For step II, the energy barriers involving the addition of one or two water molecules are higher than in absence of water. Our results also confirm that A-Ir can be applied in the dehydrogenation of various α-hydroxy carboxylic acids by the similar mechanism. Remarkably, A-Ir is also found to be efficient for the coupling reactions of various primary benzyl alcohols with ammonia to afford amides.

  15. Challenges for malaria elimination in Brazil.

    PubMed

    Ferreira, Marcelo U; Castro, Marcia C

    2016-01-01

    Brazil currently contributes 42 % of all malaria cases reported in the Latin America and the Caribbean, a region where major progress towards malaria elimination has been achieved in recent years. In 2014, malaria burden in Brazil (143,910 microscopically confirmed cases and 41 malaria-related deaths) has reached its lowest levels in 35 years, Plasmodium falciparum is highly focal, and the geographic boundary of transmission has considerably shrunk. Transmission in Brazil remains entrenched in the Amazon Basin, which accounts for 99.5 % of the country's malaria burden. This paper reviews major lessons learned from past and current malaria control policies in Brazil. A comprehensive discussion of the scientific and logistic challenges that may impact malaria elimination efforts in the country is presented in light of the launching of the Plan for Elimination of Malaria in Brazil in November 2015. Challenges for malaria elimination addressed include the high prevalence of symptomless and submicroscopic infections, emerging anti-malarial drug resistance in P. falciparum and Plasmodium vivax and the lack of safe anti-relapse drugs, the largely neglected burden of malaria in pregnancy, the need for better vector control strategies where Anopheles mosquitoes present a highly variable biting behaviour, human movement, the need for effective surveillance and tools to identify foci of infection in areas with low transmission, and the effects of environmental changes and climatic variability in transmission. Control actions launched in Brazil and results to come are likely to influence control programs in other countries in the Americas. PMID:27206924

  16. Should Pneumococcal Vaccines Eliminate Nasopharyngeal Colonization?

    PubMed Central

    Swiatlo, Edwin

    2016-01-01

    ABSTRACT  Streptococcus pneumoniae remains an important human pathogen. For more than 100 years, there have been vaccine efforts to prevent pneumococcal infection. The pneumococcal conjugate vaccines have significantly reduced invasive disease. However, these vaccines have changed pneumococcal ecology within the human nasopharynx. We suggest that elimination of the pneumococcus from the human nasopharynx can have consequences that should be considered as the next generation of pneumococcal vaccines is developed. PMID:27222469

  17. Comparing materials used in mist eliminators

    SciTech Connect

    Looney, B.; Baleno, B.; Boles, G.L.; Telow, J.

    2007-11-15

    Wet flue gas desulfurization (FGD) systems, or wet scrubbers, are notoriously capital - and maintenance-intensive. Mist eliminators are an integral part of most wet FGD systems. These are available in a variety of materials - polypropylene, fiberglass reinforced polymer (FRP), polysulfone and stainless steel. The article discusses the material properties, performance attributes and relative cost differences associated with each of these four materials. It describes the common problems with mist eliminators - fouling and corrosion. These can be minimised by routine cleaning and use of chemical additives to prevent deposition. An analysis was carried out to compare the four materials at APS Cholla power plant. As a result the facility is retrofitting its remaining wet scrubber towers in Unit 2 with mist eliminators constructed from polysulfone as each of the current ones of the existing polypropylene needs replacing. Polysulfone is cheaper to clean and components require replacing less frequently than polypropylene. Switching from stainless steel to polypropylene has proved advantageous on 22 wet scrubbers operated by PPL Montana. 5 figs. 2 tabs.

  18. Role of genomics in eliminating health disparities

    PubMed Central

    Kashyap, Meghana V; Nolan, Michael; Sprouse, Marc; Chakraborty, Ranajit; Cross, Deanna; Roby, Rhonda; Vishwanatha, Jamboor K

    2015-01-01

    The Texas Center for Health Disparities, a National Institute on Minority Health and Health Disparities Center of Excellence, presents an annual conference to discuss prevention, awareness education, and ongoing research about health disparities both in Texas and among the national population. The 2014 Annual Texas Conference on Health Disparities brought together experts in research, patient care, and community outreach on the “Role of Genomics in Eliminating Health Disparities.” Rapid advances in genomics and pharmacogenomics are leading the field of medicine to use genetics and genetic risk to build personalized or individualized medicine strategies. We are at a critical juncture of ensuring such rapid advances benefit diverse populations. Relatively few forums have been organized around the theme of the role of genomics in eliminating health disparities. The conference consisted of three sessions addressing “Gene-Environment Interactions and Health Disparities,” “Personalized Medicine and Elimination of Health Disparities,” and “Ethics and Public Policy in the Genomic Era.” This article summarizes the basic science, clinical correlates, and public health data presented by the speakers. PMID:26435701

  19. Demystifying the selection of mist eliminators

    SciTech Connect

    Fabian, P.; Cusack, R.; Hennessey, P.; Neuman, M. )

    1993-11-01

    In any process where gases and liquids come in intimate contact, mists are generated by the entrainment of liquid droplets into the gas streams. The formation of such mists often results in process inefficiencies and product loss in evaporators, knockout drums, distillation columns, and environmental scrubbers. Besides, these mists can cause serious damage to rotating equipment. hence the need to know how best to remove the liquid droplets from a misty gas stream. Today, one can select from many classes of equipment, known as mist eliminators or entrainment separators, designed to remove the liquid droplets along with any solid particles from the gas stream. Before arriving at a selection, one must weigh several important factors: The sizes of droplets that the separator must remove; The pressure drop that can be tolerated in achieving the required level of mist removal; Susceptibility of the separator to plugging by solids, if solids are present; Liquid handling capability of the separator; Whether the mist eliminator can be installed inside existing equipment, or if it requires a stand alone vessel instead; The availability of the materials of construction that are compatible with the process; and Costs of the mists eliminator itself and other required vessels, piping, instrumentation, and utilities.

  20. The near elimination of triplets in IVF.

    PubMed

    Gerris, Jan

    2007-01-01

    In Antwerp, single embryo transfers (SET) have increased, and this change in policy has seen the incidence of singletons rise from 70 to 90%, twins drop from 25 to 10%, and triplets drop from 1-2% to none at all. At a national and regional level, changes have been much more dramatic as a result of a change in the law in 2003 mandating SET. Data show a huge increase in the number of treatment cycles and a dramatic rise in SET. Rates of twins and triplets have dropped considerably. European data indicate wide differences in the incidence of triplets between countries, varying between 0% (e.g.Slovenia, Iceland, Lithuania) and 4.4% (Hungary), but almost nothing is known about the true incidence of fetal reduction. US data indicate some decrease in triplets during recent years, but certainly nowhere near elimination. These data suggest that in some countries, IVF triplets have almost been eliminated, but the problem is masked by significant fetal reductions. Where SET is not widely used, triplets are still frequent. A correlation appears to exist between the percentage of SET cycles and the incidence of triplets. It is suggested that the solution to almost totally eliminate triplets after IVF is single embryo transfer.

  1. Self-contact elimination by membrane fusion.

    PubMed

    Sumida, Grant M; Yamada, Soichiro

    2013-11-19

    Mutual, homophilic cell-cell adhesion between epithelial cells is required for proper maintenance of epithelial barrier function. Whereas opposing membranes from neighboring cells rapidly assemble junctional complexes, self-contacting membranes curiously do not, suggesting that cells have the ability to prevent the maturation of self-junctions. Using a self-contact-inducing microfabricated substrate, we show that self-contacts of normal epithelial cells are rapidly eliminated by membrane fusion between two opposing plasma membranes of a single cell. This membrane fusion is most frequently observed in E-cadherin-expressing epithelial cells, but not in fibroblasts. The efficiency of self-contact elimination depends on extracellular calcium concentration and the level of E-cadherin, suggesting that E-cadherin, although not required, enhances membrane fusion efficiency by bringing opposing membranes into close apposition to one another. Additionally, Rho-associated protein kinase inhibition decreases self-contact-induced membrane fusion of epithelial cells, suggesting that this fusion may be mechanically regulated through the actin-myosin network. This self-contact-induced membrane fusion is a key elimination mechanism for unwanted self-junctions and may be a feature of cell self-recognition. PMID:24191042

  2. Elimination of Rhodnius prolixus in Central America

    PubMed Central

    2012-01-01

    Rhodnius prolixus is one of the main vectors of Trypanosoma cruzi, causative agent of Chagas disease. In Central America, it was first discovered in 1915 in El Salvador, from where it spread northwest to Guatemala and Mexico, and southeast to Nicaragua and Costa Rica, arriving also in Honduras in the late 1950s. Indoor residual spraying (IRS) by the antimalaria services of Costa Rica prevented its spread southwards, and similar IRS programmes appear to have eliminated it from El Salvador by the late 1970s. In 1997, by resolution of the Ministers of Health of the seven Central American countries, a multinational initiative against Chagas disease (IPCA) was launched with one of the specific objectives being the elimination of R. prolixus from the region. As a result, more and more infested areas were encountered, and progressively sprayed using an IRS strategy already deployed against Triatoma infestans in the southern cone countries of South America. In 2008, Guatemala became the first of these countries to be formally certified as free of Chagas disease transmission due to R. prolixus. The other infested countries have since been similarly certified, and none of these has reported the presence of R. prolixus since June 2010. Further surveillance is required, but current evidence suggests that R. prolixus may now been eliminated from throughout the mesoamerican region, with a corresponding decline in the incidence of T. cruzi infections. PMID:22357219

  3. Malaria elimination in India and regional implications.

    PubMed

    Wangdi, Kinley; Gatton, Michelle L; Kelly, Gerard C; Banwell, Cathy; Dev, Vas; Clements, Archie C A

    2016-10-01

    The malaria situation in India is complex as a result of diverse socio-environmental conditions. India contributes a substantial burden of malaria outside sub-Saharan Africa, with the third highest Plasmodium vivax prevalence in the world. Successful malaria control in India is likely to enhance malaria elimination efforts in the region. Despite modest gains, there are many challenges for malaria elimination in India, including: varied patterns of malaria transmission in different parts of the country demanding area-specific control measures; intense malaria transmission fuelled by favourable climatic and environment factors; varying degrees of insecticide resistance of vectors; antimalarial drug resistance; a weak surveillance system; and poor national coordination of state programmes. Prevention and protection against malaria are low as a result of a weak health-care system, as well as financial and socioeconomic constraints. Additionally, the open borders of India provide a potential route of entry for artesunate-resistant parasites from southeast Asia. This situation calls for urgent dialogue around tackling malaria across borders-between India's states and neighbouring countries-through sharing of information and coordinated control and preventive measures, if we are to achieve the aim of malaria elimination in the region. PMID:27527748

  4. Transcriptome profiling reveals links between ParS/ParR, MexEF-OprN, and quorum sensing in the regulation of adaptation and virulence in Pseudomonas aeruginosa

    PubMed Central

    2013-01-01

    Background The ParS/ParR two component regulatory system plays critical roles for multidrug resistance in Pseudomonas aeruginosa. It was demonstrated that in the presence of antimicrobials, ParR enhances bacterial survival by distinct mechanisms including activation of the mexXY efflux genes, enhancement of lipopolysaccharide modification through the arn operon, and reduction of the expression of oprD porin. Results In this study, we report on transcriptomic analyses of P. aeruginosa PAO1 wild type and parS and parR mutants growing in a defined minimal medium. Our transcriptomic analysis provides the first estimates of transcript abundance for the 5570 coding genes in P. aeruginosa PAO1. Comparative transcriptomics of P. aeruginosa PAO1 and par mutants identified a total of 464 genes regulated by ParS and ParR. Results also showed that mutations in the parS/parR system abolished expression of the mexEF-oprN operon by down-regulating the regulatory gene mexS. In addition to the known effects on drug resistance genes, transcript abundances of the quorum sensing genes (rhlIR and pqsABCDE-phnAB) were higher in both parS and parR mutants. In accordance with these results, a significant portion of the ParS/ParR regulated genes belonged to the MexEF-OprN and quorum sensing regulons. Deletion of the par genes also led to increased phenazine production and swarming motility, consistent with the up-regulation of the phenazine and rhamnolipid biosynthetic genes, respectively. Conclusion Our results link the ParS/ParR two component signal transduction system to MexEF-OprN and quorum sensing systems in P. aeruginosa. These results expand our understanding of the roles of the ParS/ParR system in the regulation of gene expression in P. aeruginosa, especially in the absence of antimicrobials. PMID:24034668

  5. Mechanism of DNA Segregation in Prokaryotes: Replicon Pairing by parC of Plasmid R1

    NASA Astrophysics Data System (ADS)

    Jensen, Rasmus Bugge; Lurz, Rudi; Gerdes, Kenn

    1998-07-01

    Prokaryotic chromosomes and plasmids encode partitioning systems that are required for DNA segregation at cell division. The systems are thought to be functionally analogous to eukaryotic centromeres and to play a general role in DNA segregation. The parA system of plasmid R1 encodes two proteins ParM and ParR, and a cis-acting centromere-like site denoted parC. The ParR protein binds to parC in vivo and in vitro. The ParM protein is an ATPase that interacts with ParR specifically bound to parC. Using electron microscopy, we show here that parC mediates efficient pairing of plasmid molecules. The pairing requires binding of ParR to parC and is stimulated by the ParM ATPase. The ParM mediated stimulation of plasmid pairing is dependent on ATP hydrolysis by ParM. Using a ligation kinetics assay, we find that ParR stimulates ligation of parC-containing DNA fragments. The rate-of-ligation was increased by wild type ParM protein but not by mutant ParM protein deficient in the ATPase activity. Thus, two independent assays show that parC mediates pairing of plasmid molecules in vitro. These results are consistent with the proposal that replicon pairing is part of the mechanism of DNA segregation in prokaryotes.

  6. Pd(II)-catalysed and Hg(II)-co-catalysed oxidation of D-glucose and D-fructose by N-bromoacetamide in the presence of perchloric acid: a kinetic and mechanistic study.

    PubMed

    Singh, Ashok Kumar; Srivastava, Jaya; Rahmani, Shahla; Singh, Vineeta

    2006-02-27

    The kinetics of Pd(II)-catalysed and Hg(II)-co-catalysed oxidation of D-glucose (Glc) and D-fructose (Fru) by N-bromoacetamide (NBA) in the presence of perchloric acid using mercury(II) acetate as a scavenger for Br- ions have been studied. The results show first-order kinetics with respect to NBA at low concentrations, tending to zero order at high concentrations. First-order kinetics with respect to Pd(II) and inverse fractional order in Cl- ions throughout their variation have also been noted. The observed direct proportionality between the first-order rate constant (k1) and the reducing sugar concentration shows departure from the straight line only at very higher concentration of sugar. Addition of acetamide (NHA) decreases the first-order rate constant while the oxidation rate is not influenced by the change in the ionic strength (mu) of the medium. Variation of [Hg(OAc)2] shows a positive effect on the rate of reaction. The observed negative effect in H+ at lower concentrations tends to an insignificant effect at its higher concentrations. The first-order rate constant decreases with an increase in the dielectric constant of the medium. The various activation parameters have also been evaluated. The products of the reactions were identified as arabinonic acid and formic acid for both the hexoses. A plausible mechanism involving HOBr as the reactive oxidising species, Hg(II) as co-catalyst, and [PdCl3.S]-1 as the reactive Pd(II)-sugar complex in the rate-controlling step is proposed.

  7. Proteases in agricultural dust induce lung inflammation through PAR-1 and PAR-2 activation.

    PubMed

    Romberger, Debra J; Heires, Art J; Nordgren, Tara M; Souder, Chelsea P; West, William; Liu, Xiang-de; Poole, Jill A; Toews, Myron L; Wyatt, Todd A

    2015-08-15

    Workers exposed to aerosolized dust present in concentrated animal feeding operations (CAFOs) are susceptible to inflammatory lung diseases, such as chronic obstructive pulmonary disease. Extracts of dust collected from hog CAFOs [hog dust extract (HDE)] are potent stimulators of lung inflammatory responses in several model systems. The observation that HDE contains active proteases prompted the present study, which evaluated the role of CAFO dust proteases in lung inflammatory processes and tested whether protease-activated receptors (PARs) are involved in the signaling pathway for these events. We hypothesized that the damaging proinflammatory effect of HDE is due, in part, to the proteolytic activation of PARs, and inhibiting the proteases in HDE or disrupting PAR activation would attenuate HDE-mediated inflammatory indexes in bronchial epithelial cells (BECs), in mouse lung slices in vitro, and in a murine in vivo exposure model. Human BECs and mouse lung slice cultures stimulated with 5% HDE released significantly more of each of the cytokines measured (IL-6, IL-8, TNF-α, keratinocyte-derived chemokine/CXC chemokine ligand 1, and macrophage inflammatory protein-2/CXC chemokine ligand 2) than controls, and these effects were markedly diminished by protease inhibition. Inhibition of PARs also blunted the HDE-induced cytokine release from BECs. In addition, protease depletion inhibited HDE-induced BEC intracellular PKCα and PKCε activation. C57BL/6J mice administered 12.5% HDE intranasally, either once or daily for 3 wk, exhibited increased total cellular and neutrophil influx, bronchial alveolar fluid inflammatory cytokines, lung histopathology, and inflammatory scores compared with mice receiving protease-depleted HDE. These data suggest that proteases in dust from CAFOs are important mediators of lung inflammation, and these proteases and their receptors may provide novel targets for therapeutic intervention in CAFO dust-induced airways disease.

  8. Proteases in agricultural dust induce lung inflammation through PAR-1 and PAR-2 activation.

    PubMed

    Romberger, Debra J; Heires, Art J; Nordgren, Tara M; Souder, Chelsea P; West, William; Liu, Xiang-de; Poole, Jill A; Toews, Myron L; Wyatt, Todd A

    2015-08-15

    Workers exposed to aerosolized dust present in concentrated animal feeding operations (CAFOs) are susceptible to inflammatory lung diseases, such as chronic obstructive pulmonary disease. Extracts of dust collected from hog CAFOs [hog dust extract (HDE)] are potent stimulators of lung inflammatory responses in several model systems. The observation that HDE contains active proteases prompted the present study, which evaluated the role of CAFO dust proteases in lung inflammatory processes and tested whether protease-activated receptors (PARs) are involved in the signaling pathway for these events. We hypothesized that the damaging proinflammatory effect of HDE is due, in part, to the proteolytic activation of PARs, and inhibiting the proteases in HDE or disrupting PAR activation would attenuate HDE-mediated inflammatory indexes in bronchial epithelial cells (BECs), in mouse lung slices in vitro, and in a murine in vivo exposure model. Human BECs and mouse lung slice cultures stimulated with 5% HDE released significantly more of each of the cytokines measured (IL-6, IL-8, TNF-α, keratinocyte-derived chemokine/CXC chemokine ligand 1, and macrophage inflammatory protein-2/CXC chemokine ligand 2) than controls, and these effects were markedly diminished by protease inhibition. Inhibition of PARs also blunted the HDE-induced cytokine release from BECs. In addition, protease depletion inhibited HDE-induced BEC intracellular PKCα and PKCε activation. C57BL/6J mice administered 12.5% HDE intranasally, either once or daily for 3 wk, exhibited increased total cellular and neutrophil influx, bronchial alveolar fluid inflammatory cytokines, lung histopathology, and inflammatory scores compared with mice receiving protease-depleted HDE. These data suggest that proteases in dust from CAFOs are important mediators of lung inflammation, and these proteases and their receptors may provide novel targets for therapeutic intervention in CAFO dust-induced airways disease. PMID

  9. Proteases in agricultural dust induce lung inflammation through PAR-1 and PAR-2 activation

    PubMed Central

    Heires, Art J.; Nordgren, Tara M.; Souder, Chelsea P.; West, William; Liu, Xiang-de; Poole, Jill A.; Toews, Myron L.; Wyatt, Todd A.

    2015-01-01

    Workers exposed to aerosolized dust present in concentrated animal feeding operations (CAFOs) are susceptible to inflammatory lung diseases, such as chronic obstructive pulmonary disease. Extracts of dust collected from hog CAFOs [hog dust extract (HDE)] are potent stimulators of lung inflammatory responses in several model systems. The observation that HDE contains active proteases prompted the present study, which evaluated the role of CAFO dust proteases in lung inflammatory processes and tested whether protease-activated receptors (PARs) are involved in the signaling pathway for these events. We hypothesized that the damaging proinflammatory effect of HDE is due, in part, to the proteolytic activation of PARs, and inhibiting the proteases in HDE or disrupting PAR activation would attenuate HDE-mediated inflammatory indexes in bronchial epithelial cells (BECs), in mouse lung slices in vitro, and in a murine in vivo exposure model. Human BECs and mouse lung slice cultures stimulated with 5% HDE released significantly more of each of the cytokines measured (IL-6, IL-8, TNF-α, keratinocyte-derived chemokine/CXC chemokine ligand 1, and macrophage inflammatory protein-2/CXC chemokine ligand 2) than controls, and these effects were markedly diminished by protease inhibition. Inhibition of PARs also blunted the HDE-induced cytokine release from BECs. In addition, protease depletion inhibited HDE-induced BEC intracellular PKCα and PKCε activation. C57BL/6J mice administered 12.5% HDE intranasally, either once or daily for 3 wk, exhibited increased total cellular and neutrophil influx, bronchial alveolar fluid inflammatory cytokines, lung histopathology, and inflammatory scores compared with mice receiving protease-depleted HDE. These data suggest that proteases in dust from CAFOs are important mediators of lung inflammation, and these proteases and their receptors may provide novel targets for therapeutic intervention in CAFO dust-induced airways disease. PMID

  10. Ionic liquid catalysed reaction of thiols with α,β-unsaturated carbonyl compounds--remarkable influence of the C-2 hydrogen and the anion.

    PubMed

    Sarkar, Anirban; Roy, Sudipta Raha; Chakraborti, Asit K

    2011-04-21

    Hydrogen bond induced reactivity and selectivity control in the 1-butyl-3-methylimidazolium based ionic liquid catalysed reaction of thiols with α,β-unsaturated carbonyl compounds is reported with remarkable influence of the anion and the C-2 hydrogen in catalytic activity and reversal of selectivity.

  11. A direct approach to amines with remote stereocenters by enantioselective CuH-catalysed reductive relay hydroamination

    PubMed Central

    Zhu, Shaolin; Niljianskul, Nootaree; Buchwald, Stephen L.

    2015-01-01

    Amines with remote stereocenters (stereocenters that are three or more bonds away from the C–N bond) are important structural elements in many pharmaceutical agents and natural products. However, previously reported methods to prepare these compounds in an enantioselective manner are indirect and require multistep synthesis. Here we report a copper hydride-catalysed, enantioselective synthesis of γ- or δ-chiral amines from readily available allylic alcohols, esters, and ethers using a reductive relay hydroamination strategy (a net reductive process in which an amino group is installed at a site remote from the original C–C double bond). The protocol was suitable for substrates containing a wide range of functional groups and provided remote chiral amine products with high levels of regio- and enantioselectivity. Sequential amination of substrates containing several carbon-carbon double bonds could be achieved, demonstrating the high chemoselectivity of this process. PMID:26791897

  12. Montmorillonite-catalysed formation of RNA oligomers: the possible role of catalysis in the origins of life

    PubMed Central

    Ferris, James P

    2006-01-01

    Large deposits of montmorillonite are present on the Earth today and it is believed to have been present at the time of the origin of life and has recently been detected on Mars. It is formed by aqueous weathering of volcanic ash. It catalyses the formation of oligomers of RNA that contain monomer units from 2 to 30–50. Oligomers of this length are formed because this catalyst controls the structure of the oligomers formed and does not generate all possible isomers. Evidence of sequence-, regio- and homochiral selectivity in these oligomers has been obtained. Postulates on the role of selective versus specific catalysts on the origins of life are discussed. An introduction to the origin of life is given with an emphasis on reaction conditions based on the recent data obtained from zircons 4.0–4.5 Ga. PMID:17008218

  13. Carbene-catalysed reductive coupling of nitrobenzyl bromides and activated ketones or imines via single-electron-transfer process

    NASA Astrophysics Data System (ADS)

    Li, Bao-Sheng; Wang, Yuhuang; Proctor, Rupert S. J.; Zhang, Yuexia; Webster, Richard D.; Yang, Song; Song, Baoan; Chi, Yonggui Robin

    2016-09-01

    Benzyl bromides and related molecules are among the most common substrates in organic synthesis. They are typically used as electrophiles in nucleophilic substitution reactions. These molecules can also be activated via single-electron-transfer (SET) process for radical reactions. Representative recent progress includes α-carbon benzylation of ketones and aldehydes via photoredox catalysis. Here we disclose the generation of (nitro)benzyl radicals via N-heterocyclic carbene (NHC) catalysis under reductive conditions. The radical intermediates generated via NHC catalysis undergo formal 1,2-addition with ketones to eventually afford tertiary alcohol products. The overall process constitutes a formal polarity-inversion of benzyl bromide, allowing a direct coupling of two initially electrophilic carbons. Our study provides a new carbene-catalysed reaction mode that should enable unconventional transformation of (nitro)benzyl bromides under mild organocatalytic conditions.

  14. Carbene-catalysed reductive coupling of nitrobenzyl bromides and activated ketones or imines via single-electron-transfer process

    PubMed Central

    Li, Bao-Sheng; Wang, Yuhuang; Proctor, Rupert S. J.; Zhang, Yuexia; Webster, Richard D.; Yang, Song; Song, Baoan; Chi, Yonggui Robin

    2016-01-01

    Benzyl bromides and related molecules are among the most common substrates in organic synthesis. They are typically used as electrophiles in nucleophilic substitution reactions. These molecules can also be activated via single-electron-transfer (SET) process for radical reactions. Representative recent progress includes α-carbon benzylation of ketones and aldehydes via photoredox catalysis. Here we disclose the generation of (nitro)benzyl radicals via N-heterocyclic carbene (NHC) catalysis under reductive conditions. The radical intermediates generated via NHC catalysis undergo formal 1,2-addition with ketones to eventually afford tertiary alcohol products. The overall process constitutes a formal polarity-inversion of benzyl bromide, allowing a direct coupling of two initially electrophilic carbons. Our study provides a new carbene-catalysed reaction mode that should enable unconventional transformation of (nitro)benzyl bromides under mild organocatalytic conditions. PMID:27671606

  15. Copper-catalysed cyanoalkylative cycloetherification of alkenes to 1,3-dihydroisobenzofurans: development and application to the synthesis of citalopram.

    PubMed

    Ha, Tu M; Wang, Qian; Zhu, Jieping

    2016-09-25

    A copper-catalysed cyanoalkylative cycloetherification of alkenes was developed. Heating a solution of substituted (2-vinylphenyl)methanol in MeCN/MeOH (v/v 7/3) in the presence of a catalytic amount of copper(ii) tetrafluoroborate hydrate [Cu(BF4)2·6H2O], bathophenanthroline, K3PO4, BnOH and (tBuO)2 afforded 1,3-dihydroisobenzofurans (phthalanes) via formation of one C(sp(3))-C(sp(3)) and one C(sp(3))-O bonds. A concise synthesis of citalopram, a marketed anti-depressant drug, was accomplished by applying this novel synthetic transformation. PMID:27546372

  16. Experimental and theoretical studies on the bismuth-triflate-catalysed cycloisomerisation of 1,6,10-trienes and aryl polyenes.

    PubMed

    Godeau, Julien; Fontaine-Vive, Fabien; Antoniotti, Sylvain; Duñach, Elisabet

    2012-12-21

    Cycloisomerisation of polyenes such as diethyl geranylprenylmalonate [(E)-1 a], diethyl geranylphenylmalonate [(E)-2 a] and diethyl cinnamylgeranylmalonate [(E,E)-3 a] catalysed by bismuth triflate was studied from experimental and theoretical viewpoints. Several intermediates were isolated and characterised, and calculated transition-state structures are proposed for the three reactions. The diastereoselectivity observed during the reaction of (E)- or (Z)-2 a in favour of the formation of trans-fused bicyclic products is discussed in detail. The nature of the active catalytic species derived from bismuth triflate was also investigated, and the formation of a hybrid Lewis acid/Brønsted acid catalyst with water molecules is proposed, supported by experimental and theoretical data. PMID:23143886

  17. SPRY1 promotes the degradation of uPAR and inhibits uPAR-mediated cell adhesion and proliferation

    PubMed Central

    Liu, Xiufeng; Lan, Yan; Zhang, Di; Wang, Kai; Wang, Yao; Hua, Zi-Chun

    2014-01-01

    Urokinase plasminogen activator receptor (uPAR) is a GPI anchored cell surface protein that is closely associated with invasion, migration, and metastasis of cancer cells. Many functional extracellular proteins and transmembrane receptors interact with uPAR. However, few studies have examined the association of uPAR with cytoplasm proteins. We previously used yeast two-hybrid screening to isolate several novel uPAR-interacting cytoplasmic proteins, including Sprouty1 (SPRY1), an inhibitor of the (Ras-mitogen-activated protein kinase) MAPK pathway. In this study, we show that SPRY1 interacts with uPAR and directs it toward lysosomal-mediated degradation. Overexpression of SPRY1 decreased the cell surface and cytoplasmic uPAR protein level. Moreover, SPRY1 overexpression augmented uPAR-induced cell adhesion to vitronectin as well as proliferation of cancer cells. Our results also further support the critical role of SPRY1 contribution to tumor growth. In a subcutaneous tumor model, overexpression of SPRY1 in HCT116 or A549 xenograft in athymic nude mice led to great suppression of tumor growth. These results show that SPRY1 may affect tumor cell function through direct interaction with uPAR and promote its lysosomal degradation. PMID:25520860

  18. Waveguide arrangements based on adiabatic elimination

    DOEpatents

    Suchowski, Haim; Mrejen, Michael; Wu, Chihhui; Zhang, Xiang

    2016-09-13

    This disclosure provides systems, methods, and apparatus related to nanophotonics. In one aspect, an arrangement of waveguides includes a substrate and three waveguides. Each of the three waveguides may be a linear waveguide. A second waveguide is positioned between a first waveguide and a third waveguide. The dimensions and positions of the first, the second, and the third waveguides are specified to substantially eliminate coupling between the first waveguide and the third waveguide over a distance of about 1 millimeter to 2 millimeters along lengths of the first waveguide, the second waveguide, and the third waveguide.

  19. Should mandatory energy reporting be eliminated

    SciTech Connect

    Kendall, R.

    1981-08-01

    Energy users report problems with the Industrial Reporting Program (IRP), a joint voluntary energy-efficiency program which began in 1975. Since energy-intensive industries were already organizing voluntary reporting, the new program required unnecessary expenditures. The Reagan administration's plan to eliminate the program by not funding it is opposed by many energy managers who want the data collected to help them with their management programs. Their interest is primarily in a data base because energy costs provide adequate incentives to conserve. They also want interaction (preferably voluntary) between industry and goverment on efficiency-improvement opportunities. (DCK)

  20. Megestrol acetate NCD oral suspension--Par Pharmaceutical: megestrol acetate nanocrystal dispersion oral suspension, PAR 100.2, PAR-100.2.

    PubMed

    2007-01-01

    Par Pharmaceutical has developed megestrol acetate (Megace ES) oral suspension for the treatment of anorexia, cachexia and a significant weight loss associated with AIDS. Par Pharmaceutical used Elan Corporation's NanoCrystal Dispersion (NCD) technology to develop an advanced, concentrated formulation of megestrol acetate with improved bioavailability, more rapid onset of action, more convenient dosing and a lower dosing regimen compared with the original marketed formulation of megestrol acetate oral suspension. Patients are administered a teaspoon (5mL) of the new NCD formulation once daily, compared with a daily 20mL dosage cup of the original formulation. The new megestrol acetate NCD formulation represents a line-extension of Par's megestrol acetate oral suspension (800mg/20mL, Megace O/S) that has been marketed for anorexia, cachexia and AIDS-related weight loss since July 2001. Par's megestrol acetate is the generic version of Bristol-Myers Squibb's Megace Oral Suspension. NanoCrystal Dispersion (NCD) is a trademark of Elan Corporation. Par Pharmaceutical will market megestol acetate NCD oral suspension under the Megace brand name. The company licensed the Megace name from Bristol-Myers Squib in August 2003. The US FDA approved megestrol acetate oral suspension (625 mg/mL) in July 2005 for the treatment of anorexia, cachexia or a significant, unexplained weight loss in patients with AIDS. The NDA for the product was accepted for review by the agency in September 2004, following its submission in June of that year.Par Pharmaceutical commenced the first of two phase III clinical trials of megestrol acetate oral suspension (PAR 100.2) in cancer-induced anorexia in the first quarter of 2006. However, this trial was discontinued in September 2006 because of slow patient enrolment. The company intends to discuss future development options in this indication with the FDA.New formulations or dosage forms of megestrol acetate concentrated suspension are also in

  1. Megestrol acetate NCD oral suspension -- Par Pharmaceutical: megestrol acetate nanocrystal dispersion oral suspension, PAR 100.2, PAR-100.2.

    PubMed

    2007-01-01

    Par Pharmaceutical has developed megestrol acetate (Megace ES) oral suspension for the treatment of anorexia, cachexia and a significant weight loss associated with AIDS. Par Pharmaceutical used Elan Corporation's NanoCrystal Dispersion (NCD) technology to develop an advanced, concentrated formulation of megestrol acetate with improved bioavailability, more rapid onset of action, more convenient dosing and a lower dosing regimen compared with the original marketed formulation of megestrol acetate oral suspension. Patients are administered a teaspoon (5mL) of the new NCD formulation once daily, compared with a daily 20mL dosage cup of the original formulation. The new megestrol acetate NCD formulation represents a line-extension of Par's megestrol acetate oral suspension (800mg/20mL, Megace O/S) that has been marketed for anorexia, cachexia and AIDS-related weight loss since July 2001. Par's megestrol acetate is the generic version of Bristol-Myers Squibb's Megace Oral Suspension. NanoCrystal Dispersion (NCD) is a trademark of Elan Corporation. Par Pharmaceutical will market megestol acetate NCD oral suspension under the Megace brand name. The company licensed the Megace name from Bristol-Myers Squib in August 2003. The US FDA approved megestrol acetate oral suspension (625 mg/mL) in July 2005 for the treatment of anorexia, cachexia or a significant, unexplained weight loss in patients with AIDS. The NDA for the product was accepted for review by the agency in September 2004, following its submission in June of that year.Par Pharmaceutical commenced the first of two phase III clinical trials of megestrol acetate oral suspension (PAR 100.2) in cancer-induced anorexia in the first quarter of 2006. However, this trial was discontinued in September 2006 because of slow patient enrolment. The company intends to discuss future development options in this indication with the FDA.New formulations or dosage forms of megestrol acetate concentrated suspension are also in

  2. Self-catalysed InAs{sub 1-x}Sb{sub x} nanowires grown directly on bare Si substrates

    SciTech Connect

    Anyebe, E.A. Zhuang, Q.

    2014-12-15

    Highlights: • Self-catalysed InAs{sub 1-x}Sb{sub x} nanowires grown directly on bare Si substrates. • InAs{sub 1-x}Sb{sub x} nanowires directly grown on bare Si substrates without employing the commonly used nucleation nanowire stems which could be problematic in device applications. • Pre-deposited Indium droplets were employed to facilitate InAs{sub 1-x}Sb{sub x} nanowire nucleation and growth. • Unravels a promising route for the direct integration of InAs{sub 1-x}Sb{sub x} nanowires with the well-established Silicon platform. - Abstract: We report the self-catalysed growth of InAs{sub 1-x}Sb{sub x} nanowires directly on bare Si substrates. Vertically aligned and non-tapered InAs{sub 1-x}Sb{sub x} nanowires were realized via indium-assisted nucleation without using nanowire stems. The compositions of the InAs{sub 1-x}Sb{sub x} nanowires were determined by high resolution X-ray diffraction (HRXRD). It is observed that the geometry of the nanowires is modified by the Sb flux resulting in an almost doubling of the lateral dimension and a corresponding suppression in the axial growth of the InAs{sub 1-x}Sb{sub x} nanowires. This observation unravels a method to modify the geometry of InAs nanowire and open up a promising route for the direct integration of InAs{sub 1-x}Sb{sub x} nanowires with the well-established Si platform.

  3. Control of cleavage spindle orientation in Caenorhabditis elegans: The role of the genes par-2 and par-3

    SciTech Connect

    Cheng, N.N.; Kirby, C.M.; Kemphues, K.J.

    1995-02-01

    Polarized asymmetric divisions play important roles in the development of plants and animals. The first two embryonic cleavages of Caenorhabditis elegans provide an opportunity to study the mechanisms controlling polarized asymmetric divisions. The first cleavage is unequal, producing daughters with different sizes and fates. The daughter blastomeres divide with different orientations at the second cleavage; the anterior blastomere divides equally across the long axis of the egg, whereas the posterior blastomere divides unequally along the long axis. We report here the results of our analysis of the genes par-2 and par-3 with respect to their contribution to the polarity of these divisions. Strong loss-of-function mutations in both genes lead to an equal first cleavage and an altered second cleavage. Interestingly, the mutations exhibit striking gene-specific differences at the second cleavage. The par-2 mutations lead to transverse spindle orientations in both blastomeres, whereas par-3 mutations lead to longitudinal spindle orientations in both blastomeres. The spindle orientation defects correlate with defects in centrosome movements during both the first and the second cell cycle. Temperature shift experiments with par-2 (it5ts) indicate that the par-2(+) activity is not required after the two-cell stage. Analysis of double mutants shows that par-3 is epistatic to par-2. We propose a model wherein par-2(+) and par-3(+) act in concert during the first cell cycle to affect asymmetric modification of the cytoskeleton. This polar modification leads to different behaviors of centrosomes in the anterior and posterior and leads ultimately to blastomere-specific spindle orientations at the second cleavage. 44 refs., 5 figs., 5 tabs.

  4. Elimination of frequency noise from groundwater measurements

    SciTech Connect

    Chien, Y.M.; Bryce, R.W.; Strait, S.R.; Yeatman, R.A.

    1986-04-01

    Groundwater response to atmospheric fluctuation can be effectively removed from downhole-pressure records using the systematic approach. The technique is not as successful for removal of earth tides, due to a probable discrepancy between the actual earth tide and the theoretical earth tide. The advantage of the systematic technique is that a causative relationship is established for each component of the pressure response removed. This concept of data reduction is easily understood and well accepted. The disadvantage is that a record of the stress causing the pressure fluctuation must be obtained. This may be done by monitoring or synthesizing the stress. Frequency analysis offers a simpler way to eliminate the undesirable hydrologic fluctuations from the downhole pressure. Frequency analysis may prove to be impractical if the fluctuations being removed have broadband characteristics. A combination of the two techniques, such as eliminating the atmospheric effect with the systematic method and the earth-tide fluctuations with the frequency method, is the most effective and efficient approach.

  5. Auditing reduces accidents by eliminating unsafe practices

    SciTech Connect

    Collinge, J.A. )

    1992-08-24

    This paper reports that auditing for unsafe acts can remove the basic causes of accidents through the adoption of a proactive approach to safety. The process of auditing for unsafe acts is aimed at eliminating unsafe situations and practices by a method of constructive dialogue between managers and workers. One of the major objectives of the process is to change the cultural attitude toward safety so that it is viewed as a personal responsibility of each member of management, supervision, and the workforce. In large organizations it is common to see policy statements concerning the health and safety of employees and people associated with the business, such as contractors. In recent years, such organizations have also placed emphasis on statements related to protecting the environment. Policy guidelines for Shell companies are unambiguous: Health. The companies conduct business in such a way as to avoid harm to the health of employees and others, and to promote, as appropriate, the health of employees. Safety. Companies work on the principle that all injuries should be prevented and actively promote the high standards of safety consciousness and discipline that this principle demands. Environment. Companies pursue progressive reductions of emissions, effluents, and discharges of waste materials known to have a negative impact on the environment, with the ultimate aim of eliminating those discharges.

  6. Eliminating Cell Broadband Engine™ DMA Buffer Overflows

    NASA Astrophysics Data System (ADS)

    Murase, Masana

    This paper presents effective and efficient implementation techniques for DMA buffer overflow elimination on the Cell Broadband Engine™ (Cell/B.E.) processor. In the Cell/B.E. programming model, application developers manually issue DMA commands to transfer data from the system memory to the local memories of the Cell/B.E. cores. Although this allows us to eliminate cache misses or cache invalidation overhead, it requires careful management of the buffer arrays for DMA in the application programs to prevent DMA buffer overflows. To guard against DMA buffer overflows, we introduced safe DMA handling functions for the applications to use. To improve and minimize the performance overhead of buffer overflow prevention, we used three different optimization techniques that take advantage of SIMD operations: branch-hint-based optimizations, jump-table-based optimizations and self-modifying-based optimizations. Our optimized implementation prevents all DMA buffer overflows with minimal performance overhead, only 2.93% average slowdown in comparison to code without the buffer overflow protection.

  7. The elimination of Chagas' disease from Brazil

    PubMed Central

    MASSAD, E.

    2008-01-01

    SUMMARY On 9 June 2006 the Pan American Health Organization (PAHO) presented the Minister of Health of Brazil with the International Elimination of Transmission of Chagas' Disease Certificate. This act was the culmination of an intensive process that began in 1991 with the Southern Cone Initiative, a joint agreement between the governments of Argentina, Bolivia, Brazil, Chile, Paraguay, Uruguay and Peru, to control Chagas' disease by the elimination of the main vector, Triatoma infestans. This initiative has been highly successful and the prevalence area of the vector diminished rapidly in the last years. As a consequence, the current seroprevalence in children aged between 0 and 5 years is of the order of 10−5, a clear indication that transmission, if it is occurring, is only accidental. In this review I calculate the basic reproduction number, R0, for Chagas' disease and demonstrate that its relatively low value (1·25) explains why vectorial transmission was interrupted relatively easily. In addition, I used a mathematical model to forecast how long the remaining cases of the disease, as well as the additional vertically transmitted cases will last. PMID:18053273

  8. Scleral Buckling for Rhegmatogenous Retinal Detachment Associated with Pars Planitis

    PubMed Central

    Ahn, Jae Kyoun

    2016-01-01

    Purpose. To evaluate the surgical outcome of scleral buckling (SB) in rhegmatogenous retinal detachment (RRD) patients associated with pars planitis. Methods. Retrospective review of RRD patients (32 eyes of pars planitis RRD and 180 eyes of primary RRD) who underwent SB. We compared primary and final anatomical success rates and visual outcomes between two groups. Results. Primary and final anatomical success were achieved in 25 (78.1%) and 31 (96.8%) eyes in the pars planitis RRD group and in 167 eyes (92.7%) and 176 eyes (97.7%) in primary RRD group, respectively. Both groups showed significant visual improvement (p < 0.001) and there were no significant differences in final visual acuity. Pars planitis RRD group was associated with higher rate of postoperative proliferative vitreoretinopathy (PVR) development (12.5% versus 2.8%, p = 0.031). Pars planitis and high myopia were significant preoperative risk factors and pseudophakia was borderline risk for primary anatomical failure after adjusting for various clinical factors. Conclusions. Pars planitis associated RRD showed inferior primary anatomical outcome after SB due to postoperative PVR development. However, final anatomical and visual outcomes were favorable. RRD cases associated with pars planitis, high myopia, and pseudophakia might benefit from different surgical approaches, such as combined vitrectomy and SB. PMID:27688907

  9. Scleral Buckling for Rhegmatogenous Retinal Detachment Associated with Pars Planitis.

    PubMed

    Kim, Yong-Kyu; Yoon, Wontae; Ahn, Jae Kyoun; Park, Sung Pyo

    2016-01-01

    Purpose. To evaluate the surgical outcome of scleral buckling (SB) in rhegmatogenous retinal detachment (RRD) patients associated with pars planitis. Methods. Retrospective review of RRD patients (32 eyes of pars planitis RRD and 180 eyes of primary RRD) who underwent SB. We compared primary and final anatomical success rates and visual outcomes between two groups. Results. Primary and final anatomical success were achieved in 25 (78.1%) and 31 (96.8%) eyes in the pars planitis RRD group and in 167 eyes (92.7%) and 176 eyes (97.7%) in primary RRD group, respectively. Both groups showed significant visual improvement (p < 0.001) and there were no significant differences in final visual acuity. Pars planitis RRD group was associated with higher rate of postoperative proliferative vitreoretinopathy (PVR) development (12.5% versus 2.8%, p = 0.031). Pars planitis and high myopia were significant preoperative risk factors and pseudophakia was borderline risk for primary anatomical failure after adjusting for various clinical factors. Conclusions. Pars planitis associated RRD showed inferior primary anatomical outcome after SB due to postoperative PVR development. However, final anatomical and visual outcomes were favorable. RRD cases associated with pars planitis, high myopia, and pseudophakia might benefit from different surgical approaches, such as combined vitrectomy and SB. PMID:27688907

  10. Scleral Buckling for Rhegmatogenous Retinal Detachment Associated with Pars Planitis

    PubMed Central

    Ahn, Jae Kyoun

    2016-01-01

    Purpose. To evaluate the surgical outcome of scleral buckling (SB) in rhegmatogenous retinal detachment (RRD) patients associated with pars planitis. Methods. Retrospective review of RRD patients (32 eyes of pars planitis RRD and 180 eyes of primary RRD) who underwent SB. We compared primary and final anatomical success rates and visual outcomes between two groups. Results. Primary and final anatomical success were achieved in 25 (78.1%) and 31 (96.8%) eyes in the pars planitis RRD group and in 167 eyes (92.7%) and 176 eyes (97.7%) in primary RRD group, respectively. Both groups showed significant visual improvement (p < 0.001) and there were no significant differences in final visual acuity. Pars planitis RRD group was associated with higher rate of postoperative proliferative vitreoretinopathy (PVR) development (12.5% versus 2.8%, p = 0.031). Pars planitis and high myopia were significant preoperative risk factors and pseudophakia was borderline risk for primary anatomical failure after adjusting for various clinical factors. Conclusions. Pars planitis associated RRD showed inferior primary anatomical outcome after SB due to postoperative PVR development. However, final anatomical and visual outcomes were favorable. RRD cases associated with pars planitis, high myopia, and pseudophakia might benefit from different surgical approaches, such as combined vitrectomy and SB.

  11. Multi-scale photoacoustic remote sensing (PARS) (Conference Presentation)

    NASA Astrophysics Data System (ADS)

    Haji Reza, Parsin; Bell, Kevan; Shi, W.; Zemp, Roger J.

    2016-03-01

    We introduce a novel multi-scale photoacoustic remote sensing (PARS) imaging system. Our system can provide optical resolution details for superficial structures as well as acoustic resolution for deep-tissue imaging down to 5 cm, in a non-contact setting. PARS system does not require any contact with the sample or ultrasound coupling medium. The optical resolution PARS (OR-OARS) system uses optically focused pulsed excitation with optical detection of photoacoustic signatures using a long-coherence interrogation beam co-focused and co-scanned with the excitation spot. In the OR-PARS initial pressures are sampled right at their subsurface origin where acoustic pressures are largest. The Acoustic resolution PARS (AR-PARS) picks up the surface oscillation of the tissue caused by generated photoacoustic signal using a modified version of Michelson interferometry. By taking advantage of 4-meters polarization maintaining single-mode fiber and a green fiber laser we have generated a multi-wavelength source using stimulated Raman scattering. Remote functional imaging using this multi-wavelength excitation source and PARS detection mechanism has been demonstrated. The oxygen saturation estimations are shown for both phantom and in vivo studies. Images of blood vessel structures for an In vivo chicken embryo model is demonstrated. The Phantom studies indicates ~3µm and ~300µm lateral resolution for OR-PARS and AR-PARS respectively. To the best of our knowledge this is the first dual modality non-contact optical and acoustic resolution system used for in vivo imaging.

  12. Limnological database for Par Pond: 1959 to 1980

    SciTech Connect

    Tilly, L.J.

    1981-03-01

    A limnological database for Par Pond, a cooling reservoir for hot reactor effluent water at the Savannah River Plant, is described. The data are derived from a combination of research and monitoring efforts on Par Pond since 1959. The approximately 24,000-byte database provides water quality, primary productivity, and flow data from a number of different stations, depths, and times during the 22-year history of the Par Pond impoundment. The data have been organized to permit an interpretation of the effects of twenty years of cooling system operations on the structure and function of an aquatic ecosystem.

  13. Predicted PAR1 inhibitors from multiple computational methods

    NASA Astrophysics Data System (ADS)

    Wang, Ying; Liu, Jinfeng; Zhu, Tong; Zhang, Lujia; He, Xiao; Zhang, John Z. H.

    2016-08-01

    Multiple computational approaches are employed in order to find potentially strong binders of PAR1 from the two molecular databases: the Specs database containing more than 200,000 commercially available molecules and the traditional Chinese medicine (TCM) database. By combining the use of popular docking scoring functions together with detailed molecular dynamics simulation and protein-ligand free energy calculations, a total of fourteen molecules are found to be potentially strong binders of PAR1. The atomic details in protein-ligand interactions of these molecules with PAR1 are analyzed to help understand the binding mechanism which should be very useful in design of new drugs.

  14. An electromagnetic PIC code on the MasPar

    SciTech Connect

    MacNeice, P.

    1993-12-31

    A 3D electromagnetic particle-in-cell code has been rewritten to run on the MasPar. The original code; known as TRISTAN which was written by Oscar Buneman was rewritten in MPL and its data structure altered to suit the MasPar architecture and exploit the fully local property of the algorithm. We discuss the significant issues associated with porting the code and present a comparative analysis of the code run times on the MasPar and on the CRAY YMP and C90. Results of a simulation of the interaction of the solar wind with the earth`s magnetosphere are shown.

  15. Protease-Activated Receptor (PAR)2, but Not PAR1, Is Involved in Collateral Formation and Anti-Inflammatory Monocyte Polarization in a Mouse Hind Limb Ischemia Model

    PubMed Central

    Nossent, Anne Yael; van Oeveren-Rietdijk, Annemarie M.; de Vries, Margreet R.; Spek, C. Arnold; van Zonneveld, Anton Jan; Reitsma, Pieter H.; Hamming, Jaap F.; de Boer, Hetty C.; Versteeg, Henri H.; Quax, Paul H. A.

    2013-01-01

    Aims In collateral development (i.e. arteriogenesis), mononuclear cells are important and exist as a heterogeneous population consisting of pro-inflammatory and anti-inflammatory/repair-associated cells. Protease-activated receptor (PAR)1 and PAR2 are G-protein-coupled receptors that are both expressed by mononuclear cells and are involved in pro-inflammatory reactions, while PAR2 also plays a role in repair-associated responses. Here, we investigated the physiological role of PAR1 and PAR2 in arteriogenesis in a murine hind limb ischemia model. Methods and Results PAR1-deficient (PAR1-/-), PAR2-deficient (PAR2-/-) and wild-type (WT) mice underwent femoral artery ligation. Laser Doppler measurements revealed reduced post-ischemic blood flow recovery in PAR2-/- hind limbs when compared to WT, while PAR1-/- mice were not affected. Upon ischemia, reduced numbers of smooth muscle actin (SMA)-positive collaterals and CD31-positive capillaries were found in PAR2-/- mice when compared to WT mice, whereas these parameters in PAR1-/- mice did not differ from WT mice. The pool of circulating repair-associated (Ly6C-low) monocytes and the number of repair-associated (CD206-positive) macrophages surrounding collaterals in the hind limbs were increased in WT and PAR1-/- mice, but unaffected in PAR2-/- mice. The number of repair-associated macrophages in PAR2-/- hind limbs correlated with CD11b- and CD115-expression on the circulating monocytes in these animals, suggesting that monocyte extravasation and M-CSF-dependent differentiation into repair-associated cells are hampered. Conclusion PAR2, but not PAR1, is involved in arteriogenesis and promotes the repair-associated response in ischemic tissues. Therefore, PAR2 potentially forms a new pro-arteriogenic target in coronary artery disease (CAD) patients. PMID:23637930

  16. Evaluation of static eliminators containing polonium-210

    SciTech Connect

    Czajkowski, C.J.

    1999-01-01

    Six static eliminators containing radioactive polonium-210 microspheres were examined subsequent to a contamination incident at a commercial facility. It was found that cracked and broken microspheres were being produced and incorporated into new devices and even as received devices were potential sources of contamination. It is shown that rough handling of the devices may initiate polonium-210 leakage during or prior to service. The epoxy binder used in the devices appears to suffer significant environmental and material damage even under ambient conditions. The effects of solvents, heat, moisture, or vibration during service may accelerate this damage. The breakdown of the epoxy binder appears to be a significant contributor to the contamination by loose microspheres or microsphere fragments.

  17. Detergent water use eliminates VOC concerns

    SciTech Connect

    Chang, M.

    1996-01-01

    The article describes an electronics manufacturer`s use of detergent water and mechanical equipment (heated pressure washers and floor scrubbers) to replace volatile organic compounds. The cleaning formula development and detergent recovery system are emphasized. Detailed chemical analyses of the waste detergent water and spent filters are provided. The rationale for using detergent water; a process flow diagram for cleaning, recovery and storage; and cost considerations are summarized. At a cost of $300,000, the system removed a significant source of air emissions and enabled the plant to eliminate 30 tons of liquid hazardous waste, improve cleaning effectiveness, and save $99,000 per year in cleaning-related costs. 2 figs., 2 tabs.

  18. Elimination of the hazards from hazardous wastes.

    PubMed Central

    Gloyna, E F; Taylor, R D

    1978-01-01

    The "hazard" associated with a waste essentially controls the overall engineering approach to finding suitable alternatives for solving potential disposal problems. It should be recognized that all factors affecting environmental equilibrium must be considered, including product sales, process design, financing, pre- and end-of-pipe treatment, residuals management, and ultimate bioaccumulation of residuals. To meet this challenge, a systems approach to waste treatment and residuals disposal provides a logical approach, but this management concept requires a thorough understanding of the important physical and chemical aspects of the problem, as well as many social implications of the resulting decisions. Thus waste management within a plant necessarily involves process control, pretreatment and end-of-pipe treatment. Further, it follows that residuals management from a disposal point-of-view must ultimately embrace what is called the "multi-barrier concept." In essence, hazard elimination occurs in varying degrees during each phase of a properly engineered system. PMID:738249

  19. Error-eliminating rapid ultrasonic firing

    DOEpatents

    Borenstein, J.; Koren, Y.

    1993-08-24

    A system for producing reliable navigation data for a mobile vehicle, such as a robot, combines multiple range samples to increase the confidence'' of the algorithm in the existence of an obstacle. At higher vehicle speed, it is crucial to sample each sensor quickly and repeatedly to gather multiple samples in time to avoid a collision. Erroneous data is rejected by delaying the issuance of an ultrasonic energy pulse by a predetermined wait-period, which may be different during alternate ultrasonic firing cycles. Consecutive readings are compared, and the corresponding data is rejected if the readings differ by more than a predetermined amount. The rejection rate for the data is monitored and the operating speed of the navigation system is reduced if the data rejection rate is increased. This is useful to distinguish and eliminate noise from the data which truly represents the existence of an article in the field of operation of the vehicle.

  20. Error-eliminating rapid ultrasonic firing

    DOEpatents

    Borenstein, Johann; Koren, Yoram

    1993-08-24

    A system for producing reliable navigation data for a mobile vehicle, such as a robot, combines multiple range samples to increase the "confidence" of the algorithm in the existence of an obstacle. At higher vehicle speed, it is crucial to sample each sensor quickly and repeatedly to gather multiple samples in time to avoid a collision. Erroneous data is rejected by delaying the issuance of an ultrasonic energy pulse by a predetermined wait-period, which may be different during alternate ultrasonic firing cycles. Consecutive readings are compared, and the corresponding data is rejected if the readings differ by more than a predetermined amount. The rejection rate for the data is monitored and the operating speed of the navigation system is reduced if the data rejection rate is increased. This is useful to distinguish and eliminate noise from the data which truly represents the existence of an article in the field of operation of the vehicle.

  1. Astrocytes Control Synapse Formation, Function, and Elimination

    PubMed Central

    Chung, Won-Suk; Allen, Nicola J.; Eroglu, Cagla

    2015-01-01

    Astrocytes, through their close associations with synapses, can monitor and alter synaptic function, thus actively controlling synaptic transmission in the adult brain. Besides their important role at adult synapses, in the last three decades a number of critical findings have highlighted the importance of astrocytes in the establishment of synaptic connectivity in the developing brain. In this article, we will review the key findings on astrocytic control of synapse formation, function, and elimination. First, we will summarize our current structural and functional understanding of astrocytes at the synapse. Then, we will discuss the cellular and molecular mechanisms through which developing and mature astrocytes instruct the formation, maturation, and refinement of synapses. Our aim is to provide an overview of astrocytes as important players in the establishment of a functional nervous system. PMID:25663667

  2. Cell competition: how to eliminate your neighbours

    PubMed Central

    Amoyel, Marc; Bach, Erika A.

    2014-01-01

    A conventional view of development is that cells cooperate to build an organism. However, based on studies of Drosophila, it has been known for years that viable cells can be eliminated by their neighbours through a process termed cell competition. New studies in mammals have revealed that this process is universal and that many factors and mechanisms are conserved. During cell competition, cells with lower translation rates or those with lower levels of proteins involved in signal transduction, polarity and cellular growth can survive in a homogenous environment but are killed when surrounded by cells of higher fitness. Here, we discuss recent advances in the field as well as the mechanistic steps involved in this phenomenon, which have shed light on how and why cell competition exists in developing and adult organisms. PMID:24550108

  3. Targeting Human Transmission Biology for Malaria Elimination

    PubMed Central

    Buckee, Caroline; Marti, Matthias

    2015-01-01

    Malaria remains one of the leading causes of death worldwide, despite decades of public health efforts. The recent commitment by many endemic countries to eliminate malaria marks a shift away from programs aimed at controlling disease burden towards one that emphasizes reducing transmission of the most virulent human malaria parasite, Plasmodium falciparum. Gametocytes, the only developmental stage of malaria parasites able to infect mosquitoes, have remained understudied, as they occur in low numbers, do not cause disease, and are difficult to detect in vivo by conventional methods. Here, we review the transmission biology of P. falciparum gametocytes, featuring important recent discoveries of genes affecting parasite commitment to gametocyte formation, microvesicles enabling parasites to communicate with each other, and the anatomical site where immature gametocytes develop. We propose potential parasite targets for future intervention and highlight remaining knowledge gaps. PMID:26086192

  4. Lean for Government: Eliminating the Seven Wastes

    NASA Technical Reports Server (NTRS)

    Shepherd, Christena C.

    2012-01-01

    With shrinking budgets and a slow economy, it is becoming increasingly important for all government agencies to become more efficient. Citizens expect and deserve efficient and effective services from federal, state and local government agencies. One of the best methods to improve efficiency and eliminate waste is to institute the business process improvement methodologies known collectively as Lean; however, with reduced budgets, it may not be possible to train everyone in Lean or to engage the services of a trained consultant. It is possible, however, to raise awareness of the "Seven Wastes" of Lean in each employee, and encourage them to identify areas for improvement. Management commitment is vital to the success of these initiatives, and it is also important to develop the right metrics that will track the success of these changes.

  5. Eliminating iodine deficiency: obstacles and their removal.

    PubMed

    Padilla, Carmencita David; Fagela-Domingo, Carmelita

    2008-12-01

    Iodine deficiency remains a global concern for developing countries and some industrialised countries. Iodine deficiency is the most common cause of preventable mental retardation, posing a threat to the social and economic development of countries. Initiatives were developed and instituted to accelerate progress to achieve the goal of universal salt iodisation (USI). However, these efforts were not successful in eliminating iodine deficiency disorders (IDD) in some countries. Every year, 50 million children are born without the protection that iodine offers to the growing brain and body and about 18 million suffer some significant degree of mental impairment. The World Health Organization (WHO), United Nations Children's Fund (UNICEF) and non-governmental organisations assist to ensure that populations at risk have access to iodised salt. This paper will review the highlights of iodine deficiency and present the experiences in the various countries in Asia, i.e. assessments of the situation, action plans, and obstacles to implementation. PMID:19904447

  6. Elimination of tilmicosin in lactating ewes.

    PubMed

    Atef, M; Abo el-Sooud, K; Nahed, E; Tawfik, M

    1999-07-01

    Tilmicosin was injected subcutaneously to lactating ewes once at a dose of 10 mg kg-1 b.wt. to determine its plasma, milk, urine and ruminal juice concentrations. Tilmicosin could be detected in all those fluids 30 minutes after injection. Milk and urine concentrations were higher than those of plasma and ruminal juice. The drug was detectable in milk, urine and plasma for 9, 4 and 3 days after injection, respectively. No amount of tilmicosin could be detected in ruminal juice 12 hours following administration. The mean peak concentration of tilmicosin in plasma and milk (Cmax) were 1.29 and 9.5 micrograms ml-1 and were obtained at (Tmax) 5.235 and 15.093 hours, respectively. The drug was slowly eliminated from plasma and milk as indicated by its long half-life (t1/2el) of 15.4 and 26.2 hours, respectively. The mean binding of tilmicosin to plasma and milk proteins in vitro was 16.8% and 26.8%, respectively. The drug was not bound to ruminal juice at any extent. The rate of tilmicosin renal clearance revealed that it was correspondingly increased with higher blood concentrations. While creatinine clearance showed no significant change after tilmicosin administration. The ratio (fractional clearance) between tilmicosin renal clearance to creatinine clearance was less than one indicating that the glomerular filtration is the main pathway of elimination through kidneys. The rate of ruminal gas fermentation in ewes was inhibited after subcutaneous injection of tilmicosin at a dose of 10 mg kg-1 b.wt. The tested samples taken at different time intervals from the rumen of ewes showed a subsequent reduction in the rate of fermentation as compared to control samples. The reduction was correspondingly increased with the increase of tilmicosin concentration in ruminal juice and returned to normal thereafter.

  7. Croissance epitaxiale de GaAs sur substrats de Ge par epitaxie par faisceaux chimiques

    NASA Astrophysics Data System (ADS)

    Belanger, Simon

    La situation energetique et les enjeux environnementaux auxquels la societe est confrontee entrainent un interet grandissant pour la production d'electricite a partir de l'energie solaire. Parmi les technologies actuellement disponibles, la filiere du photovoltaique a concentrateur solaire (CPV pour concentrator photovoltaics) possede un rendement superieur et mi potentiel interessant a condition que ses couts de production soient competitifs. La methode d'epitaxie par faisceaux chimiques (CBE pour chemical beam epitaxy) possede plusieurs caracteristiques qui la rendent interessante pour la production a grande echelle de cellules photovoltaiques a jonctions multiples a base de semi-conducteurs III-V. Ce type de cellule possede la meilleure efficacite atteinte a ce jour et est utilise sur les satellites et les systemes photovoltaiques a concentrateur solaire (CPV) les plus efficaces. Une des principales forces de la technique CBE se trouve dans son potentiel d'efficacite d'utilisation des materiaux source qui est superieur a celui de la technique d'epitaxie qui est couramment utilisee pour la production a grande echelle de ces cellules. Ce memoire de maitrise presente les travaux effectues dans le but d'evaluer le potentiel de la technique CBE pour realiser la croissance de couches de GaAs sur des substrats de Ge. Cette croissance constitue la premiere etape de fabrication de nombreux modeles de cellules solaires a haute performance decrites plus haut. La realisation de ce projet a necessite le developpement d'un procede de preparation de surface pour les substrats de germanium, la realisation de nombreuses sceances de croissance epitaxiale et la caracterisation des materiaux obtenus par microscopie optique, microscopie a force atomique (AFM), diffraction des rayons-X a haute resolution (HRXRD), microscopie electronique a transmission (TEM), photoluminescence a basse temperature (LTPL) et spectrometrie de masse des ions secondaires (SIMS). Les experiences ont permis

  8. Par-4 secretion: stoichiometry of 3-arylquinoline binding to vimentin.

    PubMed

    Sviripa, Vitaliy M; Burikhanov, Ravshan; Obiero, Josiah M; Yuan, Yaxia; Nickell, Justin R; Dwoskin, Linda P; Zhan, Chang-Guo; Liu, Chunming; Tsodikov, Oleg V; Rangnekar, Vivek M; Watt, David S

    2016-01-01

    Advanced prostate tumors usually metastasize to the lung, bone, and other vital tissues and are resistant to conventional therapy. Prostate apoptosis response-4 protein (Par-4) is a tumor suppressor that causes apoptosis in therapy-resistant prostate cancer cells by binding specifically to a receptor, Glucose-regulated protein-78 (GRP78), found only on the surface of cancer cells. 3-Arylquinolines or "arylquins" induce normal cells to release Par-4 from the intermediate filament protein, vimentin and promote Par-4 secretion that targets cancer cells in a paracrine manner. A structure-activity study identified arylquins that promote Par-4 secretion, and an evaluation of arylquin binding to the hERG potassium ion channel using a [(3)H]-dofetilide binding assay permitted the identification of structural features that separated this undesired activity from the desired Par-4 secretory activity. A binding study that relied on the natural fluorescence of arylquins and that used the purified rod domain of vimentin (residues 99-411) suggested that the mechanism behind Par-4 release involved arylquin binding to multiple sites in the rod domain.

  9. Biodegradable lipids enabling rapidly eliminated lipid nanoparticles for systemic delivery of RNAi therapeutics.

    PubMed

    Maier, Martin A; Jayaraman, Muthusamy; Matsuda, Shigeo; Liu, Ju; Barros, Scott; Querbes, William; Tam, Ying K; Ansell, Steven M; Kumar, Varun; Qin, June; Zhang, Xuemei; Wang, Qianfan; Panesar, Sue; Hutabarat, Renta; Carioto, Mary; Hettinger, Julia; Kandasamy, Pachamuthu; Butler, David; Rajeev, Kallanthottathil G; Pang, Bo; Charisse, Klaus; Fitzgerald, Kevin; Mui, Barbara L; Du, Xinyao; Cullis, Pieter; Madden, Thomas D; Hope, Michael J; Manoharan, Muthiah; Akinc, Akin

    2013-08-01

    In recent years, RNA interference (RNAi) therapeutics, most notably with lipid nanoparticle-based delivery systems, have advanced into human clinical trials. The results from these early clinical trials suggest that lipid nanoparticles (LNPs), and the novel ionizable lipids that comprise them, will be important materials in this emerging field of medicine. A persistent theme in the use of materials for biomedical applications has been the incorporation of biodegradability as a means to improve biocompatibility and/or to facilitate elimination. Therefore, the aim of this work was to further advance the LNP platform through the development of novel, next-generation lipids that combine the excellent potency of the most advanced lipids currently available with biodegradable functionality. As a representative example of this novel class of biodegradable lipids, the lipid evaluated in this work displays rapid elimination from plasma and tissues, substantially improved tolerability in preclinical studies, while maintaining in vivo potency on par with that of the most advanced lipids currently available.

  10. Biodegradable Lipids Enabling Rapidly Eliminated Lipid Nanoparticles for Systemic Delivery of RNAi Therapeutics

    PubMed Central

    Maier, Martin A; Jayaraman, Muthusamy; Matsuda, Shigeo; Liu, Ju; Barros, Scott; Querbes, William; Tam, Ying K; Ansell, Steven M; Kumar, Varun; Qin, June; Zhang, Xuemei; Wang, Qianfan; Panesar, Sue; Hutabarat, Renta; Carioto, Mary; Hettinger, Julia; Kandasamy, Pachamuthu; Butler, David; Rajeev, Kallanthottathil G; Pang, Bo; Charisse, Klaus; Fitzgerald, Kevin; Mui, Barbara L; Du, Xinyao; Cullis, Pieter; Madden, Thomas D; Hope, Michael J; Manoharan, Muthiah; Akinc, Akin

    2013-01-01

    In recent years, RNA interference (RNAi) therapeutics, most notably with lipid nanoparticle-based delivery systems, have advanced into human clinical trials. The results from these early clinical trials suggest that lipid nanoparticles (LNPs), and the novel ionizable lipids that comprise them, will be important materials in this emerging field of medicine. A persistent theme in the use of materials for biomedical applications has been the incorporation of biodegradability as a means to improve biocompatibility and/or to facilitate elimination. Therefore, the aim of this work was to further advance the LNP platform through the development of novel, next-generation lipids that combine the excellent potency of the most advanced lipids currently available with biodegradable functionality. As a representative example of this novel class of biodegradable lipids, the lipid evaluated in this work displays rapid elimination from plasma and tissues, substantially improved tolerability in preclinical studies, while maintaining in vivo potency on par with that of the most advanced lipids currently available. PMID:23799535

  11. Polio elimination in Nigeria: A review

    PubMed Central

    Nasir, Usman Nakakana; Bandyopadhyay, Ananda Sankar; Montagnani, Francesca; Akite, Jacqueline Elaine; Mungu, Etaluka Blanche; Uche, Ifeanyi Valentine; Ismaila, Ahmed Mohammed

    2016-01-01

    abstract Nigeria has made tremendous strides towards eliminating polio and has been free of wild polio virus (WPV) for more than a year as of August 2015. However, sustained focus towards getting rid of all types of poliovirus by improving population immunity and enhancing disease surveillance will be needed to ensure it sustains the polio-free status. We reviewed the pertinent literature including published and unpublished, official reports and working documents of the Global Polio Eradication Initiative (GPEI) partners as well as other concerned organizations. The literature were selected based on the following criteria: published in English Language, published after year 2000, relevant content and conformance to the theme of the review and these were sorted accordingly. The challenges facing the Polio Eradication Initiative (PEI) in Nigeria were found to fall into 3 broad categories viz failure to vaccinate, failure of the Oral Polio Vaccine (OPV) and epidemiology of the virus. Failure to vaccinate resulted from insecurity, heterogeneous political support, programmatic limitation in implementation of vaccination campaigns, poor performance of vaccination teams in persistently poor performing Local Government areas and sporadic vaccine refusals in Northern Nigeria. Sub optimal effectiveness of OPV in some settings as well as the rare occurrence of VDPVs associated with OPV type 2 in areas of low immunization coverage were also found to be key issues. Some of the innovations which helped to manage the threats to the PEI include a strong government accountability frame work, change from type 2 containing OPV to bi valent OPVs for supplementary immunization activities (SIA), enhancing environmental surveillance in key states (Sokoto, Kano and Borno) along with an overall improvement in SIA quality. There has been an improvement in coverage of routine immunization and vaccination campaigns, which has resulted in Nigeria being removed from the list of endemic

  12. FtmOx1, a non-heme Fe(II) and alpha-ketoglutarate-dependent dioxygenase, catalyses the endoperoxide formation of verruculogen in Aspergillus fumigatus.

    PubMed

    Steffan, Nicola; Grundmann, Alexander; Afiyatullov, Shamil; Ruan, Hanli; Li, Shu-Ming

    2009-10-01

    Verruculogen is a tremorgenic mycotoxin and contains an endoperoxide bond. In this study, we describe the cloning, overexpression and purification of a non-heme Fe(ii) and alpha-ketoglutarate-dependent dioxygenase FtmOx1 from Aspergillus fumigatus, which catalyses the conversion of fumitremorgin B to verruculogen by inserting an endoperoxide bond between two prenyl moieties. Incubation with (18)O(2)-enriched atmosphere demonstrated that both oxygen atoms of the endoperoxide bond are derived from one molecule of O(2). FtmOx1 is the first endoperoxide-forming non-heme Fe(ii) and alpha-ketoglutarate-dependent dioxygenase reported so far. A mechanism of FtmOx1-catalysed verruculogen formation is postulated and discussed. PMID:19763315

  13. Grating lobe elimination in steerable parametric loudspeaker.

    PubMed

    Shi, Chuang; Gan, Woon-Seng

    2011-02-01

    In the past two decades, the majority of research on the parametric loudspeaker has concentrated on the nonlinear modeling of acoustic propagation and pre-processing techniques to reduce nonlinear distortion in sound reproduction. There are, however, very few studies on directivity control of the parametric loudspeaker. In this paper, we propose an equivalent circular Gaussian source array that approximates the directivity characteristics of the linear ultrasonic transducer array. By using this approximation, the directivity of the sound beam from the parametric loudspeaker can be predicted by the product directivity principle. New theoretical results, which are verified through measurements, are presented to show the effectiveness of the delay-and-sum beamsteering structure for the parametric loudspeaker. Unlike the conventional loudspeaker array, where the spacing between array elements must be less than half the wavelength to avoid spatial aliasing, the parametric loudspeaker can take advantage of grating lobe elimination to extend the spacing of ultrasonic transducer array to more than 1.5 wavelengths in a typical application.

  14. Elimination of formate production in Clostridium thermocellum

    DOE PAGES

    Rydzak, Thomas; Lynd, Lee R.; Guss, Adam M.

    2015-07-11

    We study the ability of Clostridium thermocellum to rapidly degrade cellulose and ferment resulting hydrolysis products into ethanol makes it a promising platform organism for cellulosic biofuel production via consolidated bioprocessing. Currently, however, ethanol yield are far below theoretical maximum due to branched product pathways that divert carbon and electrons towards formate, H2, lactate, acetate, and secreted amino acids. To redirect carbon and electron flux away from formate, pyruvate:formate lyase (pfl) and respective PFL-activating enzyme were deleted. Formate production in the resulting Δpfl strain was eliminated and acetate production decreased by 50% on both complex and defined medium. Growth ratemore » of Δpfl decreased by 2.9-fold on defined medium and diauxic growth was observed on complex medium. Supplementation of defined medium with 2 mM formate restored Δpfl growth rate to 80% of the parent strain. Finally, we discuss the role of pfl in metabolic engineering strategies and C1 metabolism.« less

  15. Eliminating poverty will help women most.

    PubMed

    Short, C

    1997-01-01

    It is both possible and affordable to eliminate poverty. It is also necessary to promote peaceful existence in the next century and to reduce population pressure. A key to poverty reduction is to increase equality between men and women. Women must be given access to reproductive health services and care so that they can bear their children safely and protect themselves from infection. The maternal mortality risk in Africa far exceeds that in developed countries, and many more women suffer permanent disability from child birth. At least 120 million have an unmet need for contraception, and more than 90% of AIDS cases occur among the impoverished and marginalized population of developing countries. In addition to meeting the reproductive health needs of men and women, the needs of youth must be met through coherent and coordinated efforts that support the work of all partners in development according to an agreed upon agenda crafted by developing countries. The priorities must be to 1) increase access to reproductive health information, services, and commodities and 2) to minimize the need for abortion while recognizing that women should be able to make their own moral choices and to obtain a safe abortion. The goals of the international development community for 2015 are to halve the proportion of people living in extreme poverty, to ensure reproductive health for all, and to achieve a 75% reduction in maternal mortality.

  16. Method for eliminating artifacts in CCD imagers

    DOEpatents

    Turko, B.T.; Yates, G.J.

    1992-06-09

    An electronic method for eliminating artifacts in a video camera employing a charge coupled device (CCD) as an image sensor is disclosed. The method comprises the step of initializing the camera prior to normal read out and includes a first dump cycle period for transferring radiation generated charge into the horizontal register while the decaying image on the phosphor being imaged is being integrated in the photosites, and a second dump cycle period, occurring after the phosphor image has decayed, for rapidly dumping unwanted smear charge which has been generated in the vertical registers. Image charge is then transferred from the photosites and to the vertical registers and read out in conventional fashion. The inventive method allows the video camera to be used in environments having high ionizing radiation content, and to capture images of events of very short duration and occurring either within or outside the normal visual wavelength spectrum. Resultant images are free from ghost, smear and smear phenomena caused by insufficient opacity of the registers and, and are also free from random damage caused by ionization charges which exceed the charge limit capacity of the photosites. 3 figs.

  17. Method for eliminating artifacts in CCD imagers

    DOEpatents

    Turko, Bojan T.; Yates, George J.

    1992-01-01

    An electronic method for eliminating artifacts in a video camera (10) employing a charge coupled device (CCD) (12) as an image sensor. The method comprises the step of initializing the camera (10) prior to normal read out and includes a first dump cycle period (76) for transferring radiation generated charge into the horizontal register (28) while the decaying image on the phosphor (39) being imaged is being integrated in the photosites, and a second dump cycle period (78), occurring after the phosphor (39) image has decayed, for rapidly dumping unwanted smear charge which has been generated in the vertical registers (32). Image charge is then transferred from the photosites (36) and (38) to the vertical registers (32) and read out in conventional fashion. The inventive method allows the video camera (10) to be used in environments having high ionizing radiation content, and to capture images of events of very short duration and occurring either within or outside the normal visual wavelength spectrum. Resultant images are free from ghost, smear and smear phenomena caused by insufficient opacity of the registers (28) and (32), and are also free from random damage caused by ionization charges which exceed the charge limit capacity of the photosites (36) and (37).

  18. Minimizing or eliminating refueling of nuclear reactor

    DOEpatents

    Doncals, Richard A.; Paik, Nam-Chin; Andre, Sandra V.; Porter, Charles A.; Rathbun, Roy W.; Schwallie, Ambrose L.; Petras, Diane S.

    1989-01-01

    Demand for refueling of a liquid metal fast nuclear reactor having a life of 30 years is eliminated or reduced to intervals of at least 10 years by operating the reactor at a low linear-power density, typically 2.5 kw/ft of fuel rod, rather than 7.5 or 15 kw/ft, which is the prior art practice. So that power of the same magnitude as for prior art reactors is produced, the volume of the core is increased. In addition, the height of the core and it diameter are dimensioned so that the ratio of the height to the diameter approximates 1 to the extent practicable considering the requirement of control and that the pressure drop in the coolant shall not be excessive. The surface area of a cylinder of given volume is a minimum if the ratio of the height to the diameter is 1. By minimizing the surface area, the leakage of neutrons is reduced. By reducing the linear-power density, increasing core volume, reducing fissile enrichment and optimizing core geometry, internal-core breeding of fissionable fuel is substantially enhanced. As a result, core operational life, limited by control worth requirements and fuel burnup capability, is extended up to 30 years of continuous power operation.

  19. Laccase‐catalysed polymeric dye synthesis from plant‐derived phenols for potential application in hair dyeing: Enzymatic colourations driven by homo‐ or hetero‐polymer synthesis

    PubMed Central

    Jeon, Jong‐Rok; Kim, Eun‐Ju; Murugesan, Kumarasamy; Park, Hyo‐Keun; Kim, Young‐Mo; Kwon, Jung‐Hee; Kim, Wang‐Gi; Lee, Ji‐Yeon; Chang, Yoon‐Seok

    2010-01-01

    Summary Laccase efficiently catalyses polymerization of phenolic compounds. However, knowledge on applications of polymers synthesized in this manner remains scarce. Here, the potential of laccase‐catalysed polymerization of natural phenols to form products useful in hair dyeing was investigated. All 15 tested phenols yielded coloured products after laccase treatment and colour diversity was attained by using mixtures of two phenolic monomers. After exploring colour differentiation pattern of 120 different reactions with statistical regression analysis, three monomer combinations, namely gallic acid and syringic acid, catechin and catechol, and ferulic acid and syringic acid, giving rise to brown, black, and red materials, respectively, were further characterized because such colours are commercially important for grey hair dyeing. Selected polymers could strongly absorb visible light and their hydrodynamic sizes ranged from 100 to 400 nm. Analyses of enzyme kinetic constants, liquid chromatography and electrospray ionization‐mass spectrometry (ESI‐MS) coupled with collision‐induced dissociation MS/MS indicate that both monomers in reactions involving catechin and catechol, and ferulic acid and syringic acid, are coloured by heteropolymer synthesis, but the gallic acid/syringic acid combination is based on homopolymer mixture formation. Comparison of colour parameters from these three reactions with those of corresponding artificial homopolymer mixtures also supported the idea that laccase may catalyse either hetero‐ or homo‐polymer synthesis. We finally used selected materials to dye grey hair. Each material coloured hair appropriately and the dyeing showed excellent resistance to conventional shampooing. Our study indicates that laccase‐catalysed polymerization of natural phenols is applicable to the development of new cosmetic pigments. PMID:21255331

  20. Laccase-catalysed polymeric dye synthesis from plant-derived phenols for potential application in hair dyeing: Enzymatic colourations driven by homo- or hetero-polymer synthesis.

    PubMed

    Jeon, Jong-Rok; Kim, Eun-Ju; Murugesan, Kumarasamy; Park, Hyo-Keun; Kim, Young-Mo; Kwon, Jung-Hee; Kim, Wang-Gi; Lee, Ji-Yeon; Chang, Yoon-Seok

    2010-05-01

    Laccase efficiently catalyses polymerization of phenolic compounds. However, knowledge on applications of polymers synthesized in this manner remains scarce. Here, the potential of laccase-catalysed polymerization of natural phenols to form products useful in hair dyeing was investigated. All 15 tested phenols yielded coloured products after laccase treatment and colour diversity was attained by using mixtures of two phenolic monomers. After exploring colour differentiation pattern of 120 different reactions with statistical regression analysis, three monomer combinations, namely gallic acid and syringic acid, catechin and catechol, and ferulic acid and syringic acid, giving rise to brown, black, and red materials, respectively, were further characterized because such colours are commercially important for grey hair dyeing. Selected polymers could strongly absorb visible light and their hydrodynamic sizes ranged from 100 to 400 nm. Analyses of enzyme kinetic constants, liquid chromatography and electrospray ionization-mass spectrometry (ESI-MS) coupled with collision-induced dissociation MS/MS indicate that both monomers in reactions involving catechin and catechol, and ferulic acid and syringic acid, are coloured by heteropolymer synthesis, but the gallic acid/syringic acid combination is based on homopolymer mixture formation. Comparison of colour parameters from these three reactions with those of corresponding artificial homopolymer mixtures also supported the idea that laccase may catalyse either hetero- or homo-polymer synthesis. We finally used selected materials to dye grey hair. Each material coloured hair appropriately and the dyeing showed excellent resistance to conventional shampooing. Our study indicates that laccase-catalysed polymerization of natural phenols is applicable to the development of new cosmetic pigments.

  1. Enzyme-catalysed deposition of ultrathin silver shells on gold nanorods: a universal and highly efficient signal amplification strategy for translating immunoassay into a litmus-type test.

    PubMed

    Yang, Xinjian; Gao, Zhiqiang

    2015-04-25

    On the basis of enzyme-catalysed reduction of silver ions and consequent deposition of ultrathin silver shells on gold nanorods, a highly efficient signal amplification method for immunoassay is developed. For a model analyte prostate-specific antigen, a 10(4)-fold improvement over conventional enzyme-linked immunosorbent assay is accomplished by leveraging on the cumulative nature of the enzymatic reaction and the sensitive response of plasnomic gold nanorods to the deposition the silver shells.

  2. Cyclic reactions catalysed by detergent-dispersed and reconstituted transhydrogenase from beef-heart mitochondria; implications for the mechanism of proton translocation.

    PubMed

    Sazanov, L A; Jackson, J B

    1995-10-10

    Transhydrogenase from beef-heart mitochondria was solubilised with Triton X-100 and purified by column chromatography. The detergent-dispersed enzyme catalysed the reduction of acetylpyridine adenine dinucleotide (AcPdAD+) by NADH, but only in the presence of NADP+. Experiments showed that this reaction was cyclic; NADP(H), whilst remaining bound to the enzyme, was alternately reduced by NADH and oxidised by AcPdAD+. A period of incubation of the enzyme with NADPH at pH 6.0 led to inhibition of the simple transhydrogenation reaction between AcPdAD+ and NADPH. However, after such treatment, transhydrogenase acquired the ability to catalyse the (NADPH-dependent) reduction of AcPdAD+ by NADH. It is suggested that this is a similar cycle to the one described above. Evidently, the binding affinity for NADP+ increases as a consequence of the inhibition process resulting from prolonged incubation with NADPH. The pH dependences of simple and cyclic transhydrogenation reactions are described. Though more complex than those in Escherichia coli transhydrogenase, they are consistent with the view [Hutton, M., Day, J.M., Bizouarn, T. and Jackson, J.B. (1994) Eur. J. Biochem. 219, 1041-1051] that, also in the mitochondrial enzyme, binding and release of NADP+ and NADPH are accompanied by binding and release of a proton. The enzyme was successfully reconstituted into liposomes by a cholate dilution procedure. The proteoliposomes catalysed cyclic NADPH-dependent reduction of AcPdAD+ by NADH only when they were tightly coupled. However, they catalysed cyclic NADP(+)-dependent reduction of AcPdAD+ by NADH only when they were uncoupled eg. by addition of carbonylcyanide-p-trifluoromethoxyphenyl hydrazone.(ABSTRACT TRUNCATED AT 250 WORDS)

  3. Oxidation and β-Alkylation of Alcohols Catalysed by Iridium(I) Complexes with Functionalised N-Heterocyclic Carbene Ligands.

    PubMed

    Jiménez, M Victoria; Fernández-Tornos, Javier; Modrego, F Javier; Pérez-Torrente, Jesús J; Oro, Luis A

    2015-12-01

    The borrowing hydrogen methodology allows for the use of alcohols as alkylating agents for CC bond forming processes offering significant environmental benefits over traditional approaches. Iridium(I)-cyclooctadiene complexes having a NHC ligand with a O- or N-functionalised wingtip efficiently catalysed the oxidation and β-alkylation of secondary alcohols with primary alcohols in the presence of a base. The cationic complex [Ir(NCCH3 )(cod)(MeIm(2- methoxybenzyl))][BF4 ] (cod=1,5-cyclooctadiene, MeIm=1-methylimidazolyl) having a rigid O-functionalised wingtip, shows the best catalyst performance in the dehydrogenation of benzyl alcohol in acetone, with an initial turnover frequency (TOF0 ) of 1283 h(-1) , and also in the β-alkylation of 2-propanol with butan-1-ol, which gives a conversion of 94 % in 10 h with a selectivity of 99 % for heptan-2-ol. We have investigated the full reaction mechanism including the dehydrogenation, the cross-aldol condensation and the hydrogenation step by DFT calculations. Interestingly, these studies revealed the participation of the iridium catalyst in the key step leading to the formation of the new CC bond that involves the reaction of an O-bound enolate generated in the basic medium with the electrophilic aldehyde.

  4. Oxidation of indole-3-acetic acid by dioxygen catalysed by plant peroxidases: specificity for the enzyme structure.

    PubMed

    Savitsky, P A; Gazaryan, I G; Tishkov, V I; Lagrimini, L M; Ruzgas, T; Gorton, L

    1999-06-15

    Indole-3-acetic acid (IAA) can be oxidized via two mechanisms: a conventional hydrogen-peroxide-dependent pathway, and one that is hydrogen-peroxide-independent and requires oxygen. It has been shown here for the first time that only plant peroxidases are able to catalyse the reaction of IAA oxidation with molecular oxygen. Cytochrome c peroxidase (CcP), fungal peroxidases (manganese-dependent peroxidase, lignin peroxidase and Arthromyces ramosus peroxidase) and microperoxidase were essentially inactive towards IAA in the absence of added H2O2. An analysis of amino acid sequences allowed five structurally similar fragments to be identified in auxin-binding proteins and plant peroxidases. The corresponding fragments in CcP and fungal peroxidases showed no similarity with auxin-binding proteins. Five structurally similar fragments form a subdomain including the catalytic centre and two residues highly conserved among 'classical' plant peroxidases only, namely His-40 and Trp-117. The subdomain identified above with the two residues might be responsible for the oxidation of the physiological substrate of classical plant peroxidases, IAA. PMID:10359640

  5. Identification and characterization of two families of F420H2-dependent reductases from Mycobacteria that catalyse aflatoxin degradation

    PubMed Central

    Taylor, Matthew C; Jackson, Colin J; Tattersall, David B; French, Nigel; Peat, Thomas S; Newman, Janet; Briggs, Lyndall J; Lapalikar, Gauri V; Campbell, Peter M; Scott, Colin; Russell, Robyn J; Oakeshott, John G

    2010-01-01

    Aflatoxins are polyaromatic mycotoxins that contaminate a range of food crops as a result of fungal growth and contribute to serious health problems in the developing world because of their toxicity and mutagenicity. Although relatively resistant to biotic degradation, aflatoxins can be metabolized by certain species of Actinomycetales. However, the enzymatic basis for their breakdown has not been reported until now. We have identified nine Mycobacterium smegmatis enzymes that utilize the deazaflavin cofactor F420H2 to catalyse the reduction of the α,β-unsaturated ester moiety of aflatoxins, activating the molecules for spontaneous hydrolysis and detoxification. These enzymes belong to two previously uncharacterized F420H2 dependent reductase (FDR-A and -B) families that are distantly related to the flavin mononucleotide (FMN) dependent pyridoxamine 5′-phosphate oxidases (PNPOxs). We have solved crystal structures of an enzyme from each FDR family and show that they, like the PNPOxs, adopt a split barrel protein fold, although the FDRs also possess an extended and highly charged F420H2 binding groove. A general role for these enzymes in xenobiotic metabolism is discussed, including the observation that the nitro-reductase Rv3547 from Mycobacterium tuberculosis that is responsible for the activation of bicyclic nitroimidazole prodrugs belongs to the FDR-A family. PMID:20807200

  6. Oxidation and β-Alkylation of Alcohols Catalysed by Iridium(I) Complexes with Functionalised N-Heterocyclic Carbene Ligands.

    PubMed

    Jiménez, M Victoria; Fernández-Tornos, Javier; Modrego, F Javier; Pérez-Torrente, Jesús J; Oro, Luis A

    2015-12-01

    The borrowing hydrogen methodology allows for the use of alcohols as alkylating agents for CC bond forming processes offering significant environmental benefits over traditional approaches. Iridium(I)-cyclooctadiene complexes having a NHC ligand with a O- or N-functionalised wingtip efficiently catalysed the oxidation and β-alkylation of secondary alcohols with primary alcohols in the presence of a base. The cationic complex [Ir(NCCH3 )(cod)(MeIm(2- methoxybenzyl))][BF4 ] (cod=1,5-cyclooctadiene, MeIm=1-methylimidazolyl) having a rigid O-functionalised wingtip, shows the best catalyst performance in the dehydrogenation of benzyl alcohol in acetone, with an initial turnover frequency (TOF0 ) of 1283 h(-1) , and also in the β-alkylation of 2-propanol with butan-1-ol, which gives a conversion of 94 % in 10 h with a selectivity of 99 % for heptan-2-ol. We have investigated the full reaction mechanism including the dehydrogenation, the cross-aldol condensation and the hydrogenation step by DFT calculations. Interestingly, these studies revealed the participation of the iridium catalyst in the key step leading to the formation of the new CC bond that involves the reaction of an O-bound enolate generated in the basic medium with the electrophilic aldehyde. PMID:26493780

  7. Optimisation of flavour ester biosynthesis in an aqueous system of coconut cream and fusel oil catalysed by lipase.

    PubMed

    Sun, Jingcan; Yu, Bin; Curran, Philip; Liu, Shao-Quan

    2012-12-15

    Coconut cream and fusel oil, two low-cost natural substances, were used as starting materials for the biosynthesis of flavour-active octanoic acid esters (ethyl-, butyl-, isobutyl- and (iso)amyl octanoate) using lipase Palatase as the biocatalyst. The Taguchi design method was used for the first time to optimize the biosynthesis of esters by a lipase in an aqueous system of coconut cream and fusel oil. Temperature, time and enzyme amount were found to be statistically significant factors and the optimal conditions were determined to be as follows: temperature 30°C, fusel oil concentration 9% (v/w), reaction time 24h, pH 6.2 and enzyme amount 0.26 g. Under the optimised conditions, a yield of 14.25mg/g (based on cream weight) and signal-to-noise (S/N) ratio of 23.07 dB were obtained. The results indicate that the Taguchi design method was an efficient and systematic approach to the optimisation of lipase-catalysed biological processes.

  8. The carotenoid cleavage dioxygenase CCD2 catalysing the synthesis of crocetin in spring crocuses and saffron is a plastidial enzyme.

    PubMed

    Ahrazem, Oussama; Rubio-Moraga, Angela; Berman, Judit; Capell, Teresa; Christou, Paul; Zhu, Changfu; Gómez-Gómez, Lourdes

    2016-01-01

    The apocarotenoid crocetin and its glycosylated derivatives, crocins, confer the red colour to saffron. Crocetin biosynthesis in saffron is catalysed by the carotenoid cleavage dioxygenase CCD2 (AIG94929). No homologues have been identified in other plant species due to the very limited presence of crocetin and its derivatives in the plant kingdom. Spring Crocus species with yellow flowers accumulate crocins in the stigma and tepals. Four carotenoid CCDs, namely CaCCD1, CaCCD2 and CaCCD4a/b and CaCCD4c were first cloned and characterized. CaCCD2 was localized in plastids, and a longer CCD2 version, CsCCD2L, was also localized in this compartment. The activity of CaCCD2 was assessed in Escherichia coli and in a stable rice gene function characterization system, demonstrating the production of crocetin in both systems. The expression of all isolated CCDs was evaluated in stigma and tepals at three key developmental stages in relation with apocarotenoid accumulation. CaCCD2 expression parallels crocin accumulation, but C14 apocarotenoids most likely are associated to the CaCCD1 activity in Crocus ancyrensis flowers. The specific CCD2 localization and its membrane interaction will contribute to the development of a better understanding of the mechanism of crocetin biosynthesis and regulation in the chromoplast. PMID:26377696

  9. Lipase-catalysed acylation of starch and determination of the degree of substitution by methanolysis and GC

    PubMed Central

    2010-01-01

    Background Natural polysaccharides such as starch are becoming increasingly interesting as renewable starting materials for the synthesis of biodegradable polymers using chemical or enzymatic methods. Given the complexity of polysaccharides, the analysis of reaction products is challenging. Results Esterification of starch with fatty acids has traditionally been monitored by saponification and back-titration, but in our experience this method is unreliable. Here we report a novel GC-based method for the fast and reliable quantitative determination of esterification. The method was used to monitor the enzymatic esterification of different starches with decanoic acid, using lipase from Thermomyces lanuginosus. The reaction showed a pronounced optimal water content of 1.25 mL per g starch, where a degree of substitution (DS) of 0.018 was obtained. Incomplete gelatinization probably accounts for lower conversion with less water. Conclusions Lipase-catalysed esterification of starch is feasible in aqueous gel systems, but attention to analytical methods is important to obtain correct DS values. PMID:21114817

  10. Identification of Dehalobacter reductive dehalogenases that catalyse dechlorination of chloroform, 1,1,1-trichloroethane and 1,1-dichloroethane

    PubMed Central

    Tang, Shuiquan; Edwards, Elizabeth A.

    2013-01-01

    Two novel reductive dehalogenases (RDases) that are highly similar to each other but catalyse distinct dechlorination reactions were identified from Dehalobacter-containing mixed cultures. These two RDases were partially purified from crude protein extracts of anaerobic dechlorinating enrichment cultures using blue native polyacrylamide gel electrophoresis. Gel slices were assayed for dechlorinating activity, and associated proteins were identified using liquid chromatography tandem mass spectrometry with the metagenome of the parent culture as the reference database. The two RDases identified, annotated as CfrA and DcrA, share an amino acid identity of 95.2 per cent, but use different substrates: CfrA dechlorinates chloroform (CF) and 1,1,1-trichloroethane (1,1,1-TCA), but not 1,1-dichloroethane; DcrA dechlorinates 1,1-dichloroethane, but not CF or 1,1,1-TCA. These two novel RDases share no more than 40 per cent amino acid identity to any other known or putative RDases, but both have a twin-arginine motif and two iron–sulfur binding motifs conserved in most RDases. Peptides specific to two putative membrane anchor proteins, annotated as CfrB and DcrB, were also detected in gel slices. PMID:23479748

  11. Oxidation of indole-3-acetic acid by dioxygen catalysed by plant peroxidases: specificity for the enzyme structure.

    PubMed Central

    Savitsky, P A; Gazaryan, I G; Tishkov, V I; Lagrimini, L M; Ruzgas, T; Gorton, L

    1999-01-01

    Indole-3-acetic acid (IAA) can be oxidized via two mechanisms: a conventional hydrogen-peroxide-dependent pathway, and one that is hydrogen-peroxide-independent and requires oxygen. It has been shown here for the first time that only plant peroxidases are able to catalyse the reaction of IAA oxidation with molecular oxygen. Cytochrome c peroxidase (CcP), fungal peroxidases (manganese-dependent peroxidase, lignin peroxidase and Arthromyces ramosus peroxidase) and microperoxidase were essentially inactive towards IAA in the absence of added H2O2. An analysis of amino acid sequences allowed five structurally similar fragments to be identified in auxin-binding proteins and plant peroxidases. The corresponding fragments in CcP and fungal peroxidases showed no similarity with auxin-binding proteins. Five structurally similar fragments form a subdomain including the catalytic centre and two residues highly conserved among 'classical' plant peroxidases only, namely His-40 and Trp-117. The subdomain identified above with the two residues might be responsible for the oxidation of the physiological substrate of classical plant peroxidases, IAA. PMID:10359640

  12. Dioxygenase-catalysed oxidation of disubstituted benzene substrates: benzylic monohydroxylation versus aryl cis-dihydroxylation and the meta effect.

    PubMed

    Boyd, Derek R; Sharma, Narain D; Bowers, Nigel I; Dalton, Howard; Garrett, Mark D; Harrison, John S; Sheldrake, Gary N

    2006-09-01

    Biotransformations of a series of ortho-, meta- and para-substituted ethylbenzene and propylbenzene substrates have been carried out, using Pseudomonas putida UV4, a source of toluene dioxygenase (TDO). The ortho- and para-substituted alkylbenzene substrates yielded, exclusively, the corresponding enantiopure cis-dihydrodiols of the same absolute configuration. However, the meta isomers, generally, gave benzylic alcohol bioproducts, in addition to the cis-dihydrodiols (the meta effect). The benzylic alcohols were of identical (R) absolute configuration but enantiomeric excess values were variable. The similar (2R) absolute configurations of the cis-dihydrodiols are consistent with both the ethyl and propyl groups having dominant stereodirecting effects over the other substituents. The model used earlier, to predict the regio- and stereo-chemistry of cis-dihydrodiol bioproducts derived from substituted benzene substrates has been refined, to take account of non-symmetric substituents like ethyl or propyl groups. The formation of benzylic hydroxylation products, from meta-substituted benzene substrates, without further cis-dihydroxylation to yield triols provides a further example of the meta effect during toluene dioxygenase-catalysed oxidations.

  13. Sn-Beta zeolites with borate salts catalyse the epimerization of carbohydrates via an intramolecular carbon shift

    PubMed Central

    Gunther, William R.; Wang, Yuran; Ji, Yuewei; Michaelis, Vladimir K.; Hunt, Sean T.; Griffin, Robert G.; Román-Leshkov, Yuriy

    2012-01-01

    Carbohydrate epimerization is an essential technology for the widespread production of rare sugars. In contrast to other enzymes, most epimerases are only active on sugars substituted with phosphate or nucleotide groups, thus drastically restricting their use. Here we show that Sn-Beta zeolite in the presence of sodium tetraborate catalyses the selective epimerization of aldoses in aqueous media. Specifically, a 5 wt% aldose (for example, glucose, xylose or arabinose) solution with a 4:1 aldose:sodium tetraborate molar ratio reacted with catalytic amounts of Sn-Beta yields near-equilibrium epimerization product distributions. The reaction proceeds by way of a 1,2 carbon shift wherein the bond between C-2 and C-3 is cleaved and a new bond between C-1 and C-3 is formed, with C-1 moving to the C-2 position with an inverted configuration. This work provides a general method of performing carbohydrate epimerizations that surmounts the main disadvantages of current enzymatic and inorganic processes. PMID:23047667

  14. Palladium-catalysed directed C-H activation by anilides and ureas; water participation in a general base mechanism.

    PubMed

    Rauf, Waqar; Brown, John M

    2016-06-21

    C-H activation plays a central role in organometallic catalysis. Concerted metallation-deprotonation (CMD) has been dominant as the pathway for C-H bond cleavage. In the course of studying the mechanism of C-H activation of arylamides and arylureas with Pd complexes as part of catalytic oxidative Heck reactions, DFT calculations were carried out. The turnover-limiting C-H activation is acid-catalysed and can occur readily in the absence of acetate or other coordinating bases. The calculations simulated experiment, so that ligated sulfonate and water, both previously observed by X-ray characterization, were incorporated in the model. A Wheland-type complex between acetanilide and Pd was readily located, but the reactive C-H and the coordinated sulfonate were poorly placed for intramolecular proton transfer. Involvement of a water molecule coordinated to sulfonate provides a low-energy pathway to the palladacycle. The relative reactivity of substituted acetanilides and arylureas according to this model fits well with existing literature. General-base catalysis as described here has broader potential. PMID:27184358

  15. Enzyme reaction engineering: synthesis of antibiotics catalysed by stabilized penicillin G acylase in the presence of organic cosolvents.

    PubMed

    Fernandez-Lafuente, R; Rosell, C M; Guisán, J M

    1991-11-01

    By using very active and very stable penicillin G acylase (PGA)--agarose derivatives we have studied the industrial design of equilibrium-controlled synthesis of lactamic antibiotics. In the presence of high concentrations of organic cosolvents we have carried out the direct enzymatic condensation of phenylacetic acid and 6-aminopenicillanic acid to yield the model antibiotic penicillin G. We have mainly studied the integrated effect of different variables that define the reaction medium on a number of parameters of industrial interest:time course of antibiotic synthesis, highest synthetic yields, stability of the catalyst, and solubility and stability of substrates and products. The main variables tested were the nature and concentration of the organic cosolvent, pH, and temperature. The effects of the variables tested on different parameters were quite different and sometimes opposite. Hence, the optimal experimental conditions for antibiotic synthesis catalysed by PGA were established, as a compromise solution, in order to obtain good values for every parameter of industrial interest. These conditions seem to be important parameters for scale-up (e.g. we have been able to reach more than 95% of synthetic yields with productivities around 0.5 tons of model antibiotic per year per liter of catalyst).

  16. A DFT study of the mechanism of NHC catalysed annulation reactions involving α,β-unsaturated acyl azoliums and β-naphthol.

    PubMed

    Aurell, M José; Domingo, Luis R; Arnó, Manuel; Zaragozá, Ramón J

    2016-09-21

    The mechanism of NHC catalysed annulation reactions involving an α,β-unsaturated acyl azolium and β-naphthol has been studied using DFT methods at the MPWB1K/6-311G(d,p) level in toluene. For the C-C bond formation step, which corresponds to the rate- and stereo-determining step of this NHC catalysed reaction, the two competitive addition modes, i.e. the 1,2- and the 1,4-additions, have been studied. In toluene, acyl azolium forms an ion pair (IP) with the counterion chloride anion. Interestingly, β-naphthol forms a hydrogen bond with the chloride anion of IP, increasing the nucleophilic character of β-naphthol and the electrophilic character of the acyl azolium moiety. For the first time, the transition state (TS) associated with the 1,2-addition is found and characterised. An analysis of the activation Gibbs free energies involved in the two competitive pathways makes it possible to rule out the pathway associated with the 1,2-addition. The relative Gibbs free energy of stereoisomeric TSs present in the 1,4-additions, accounts for the experimentally observed stereoselectivity. Finally, a comparative study of the pathways associated with the 1,2- and the 1,4-addition of β-naphthalenethiol to the acyl azolium moiety of IP accounts for the low reactivity of β-naphthalenethiol in these NHC catalysed annulation reactions involving α,β-unsaturated acyl azoliums.

  17. A DFT study of the mechanism of NHC catalysed annulation reactions involving α,β-unsaturated acyl azoliums and β-naphthol.

    PubMed

    Aurell, M José; Domingo, Luis R; Arnó, Manuel; Zaragozá, Ramón J

    2016-09-21

    The mechanism of NHC catalysed annulation reactions involving an α,β-unsaturated acyl azolium and β-naphthol has been studied using DFT methods at the MPWB1K/6-311G(d,p) level in toluene. For the C-C bond formation step, which corresponds to the rate- and stereo-determining step of this NHC catalysed reaction, the two competitive addition modes, i.e. the 1,2- and the 1,4-additions, have been studied. In toluene, acyl azolium forms an ion pair (IP) with the counterion chloride anion. Interestingly, β-naphthol forms a hydrogen bond with the chloride anion of IP, increasing the nucleophilic character of β-naphthol and the electrophilic character of the acyl azolium moiety. For the first time, the transition state (TS) associated with the 1,2-addition is found and characterised. An analysis of the activation Gibbs free energies involved in the two competitive pathways makes it possible to rule out the pathway associated with the 1,2-addition. The relative Gibbs free energy of stereoisomeric TSs present in the 1,4-additions, accounts for the experimentally observed stereoselectivity. Finally, a comparative study of the pathways associated with the 1,2- and the 1,4-addition of β-naphthalenethiol to the acyl azolium moiety of IP accounts for the low reactivity of β-naphthalenethiol in these NHC catalysed annulation reactions involving α,β-unsaturated acyl azoliums. PMID:27530598

  18. Par Pond vegetation status Summer 1995 -- June survey descriptive summary

    SciTech Connect

    Mackey, H.E. Jr.; Riley, R.S.

    1995-06-01

    The water level of Par Pond was lowered approximately 20 feet in mid-1991 in order to protect downstream residents from possible dam failure suggested by subsidence on the downstream slope of the dam and to repair the dam. This lowering exposed both emergent and nonemergent macrophyte beds to drying conditions resulting in extensive losses. A survey of the shoreline aquatic plant communities in June 1995, three months after the refilling of Par Pond to approximately 200 feet above mean sea level, indicated that much of the original plant communities and the intermediate shoreline communities present on the exposed sediments have been lost. The extensive old-field and emergent marsh communities that were present on the exposed shoreline during the drawdown have been flooded and much of the pre-drawdown Par Pond aquatic plant communities have not had sufficient time for re-establishment. The shoreline does, however, have extensive beds of maidencane which extend from the shoreline margin to areas as deep as 2 and perhaps 3 meters. Scattered individual plants of lotus and watershield are common and may indicate likely directions of future wetland development in Par Pond. In addition, within isolated coves, which apparently received ground water seepage and/or stream surface flows during the period of the Par Pond draw down, extensive beds of waterlilies and spike rush are common. Invasion of willow and red maple occurred along the lake shoreline as well. Although not absent from this survey, evidence of the extensive redevelopment of the large cattail and eel grass beds was not observed in this first survey of Par Pond. Future surveys during the growing seasons of 1995, 1996, and 1997 along with the evaluation of satellite date to map the areal extent of the macrophyte beds of Par Pond are planned.

  19. Pars Planitis: Epidemiology, Clinical Characteristics, Management and Visual Prognosis.

    PubMed

    Ozdal, Pinar Cakar; Berker, Nilufer; Tugal-Tutkun, Ilknur

    2015-01-01

    Pars planitis is an idiopathic chronic intermediate uveitis which predominantly affects children and adolescents, and accounts for 5-26.7% of pediatric uveitis. Although an autoimmune process with a genetic predisposition has been suggested, its etiology still remains unknown. The most common presenting symptoms are floaters and blurred vision. Diffuse vitreous cells, haze, snowballs and snowbanks are typical findings of pars planitis. Peripheral retinal vasculitis, optic disc edema and anterior segment inflammation are other well-known findings. Although pars planitis is known to be a benign form of uveitis in most cases, it may become a potentially blinding disease due to complications including cataract, cystoid macular edema, vitreous opacities and optic disc edema. Cystoid macular edema is the most common cause of visual morbidity. Band keratopathy, epiretinal membrane formation, vitreous condensation, neovascularizations, vitreous hemorrhage, retinal detachment, cyclitic membranes, glaucoma and amblyopia may develop as a consequence of the chronic course of the disease. Exclusion of infectious and non-infectious causes which may present with intermediate uveitis is of utmost importance before starting treatment. Treatment of pars planitis has been a controversial issue. There is no consensus specifically for treatment of cases with minimal inflammation and relatively good visual acuity. However, current experience shows that pars planitis may cause severe inflammation and needs an aggressive treatment. A stepladder approach including corticosteroids, immunosupressive agents, anti-tumor necrosis factor-alpha and pars plana vitrectomy and/or laser photocoagulation is the most commonly used method for treatment of pars planitis. Adequate control of inflammation and prompt detection of associated complications are crucial in order to improve the overall prognosis of the disease. PMID:27051493

  20. Pars Planitis: Epidemiology, Clinical Characteristics, Management and Visual Prognosis

    PubMed Central

    Ozdal, Pinar Cakar; Berker, Nilufer; Tugal-Tutkun, Ilknur

    2015-01-01

    Pars planitis is an idiopathic chronic intermediate uveitis which predominantly affects children and adolescents, and accounts for 5-26.7% of pediatric uveitis. Although an autoimmune process with a genetic predisposition has been suggested, its etiology still remains unknown. The most common presenting symptoms are floaters and blurred vision. Diffuse vitreous cells, haze, snowballs and snowbanks are typical findings of pars planitis. Peripheral retinal vasculitis, optic disc edema and anterior segment inflammation are other well-known findings. Although pars planitis is known to be a benign form of uveitis in most cases, it may become a potentially blinding disease due to complications including cataract, cystoid macular edema, vitreous opacities and optic disc edema. Cystoid macular edema is the most common cause of visual morbidity. Band keratopathy, epiretinal membrane formation, vitreous condensation, neovascularizations, vitreous hemorrhage, retinal detachment, cyclitic membranes, glaucoma and amblyopia may develop as a consequence of the chronic course of the disease. Exclusion of infectious and non-infectious causes which may present with intermediate uveitis is of utmost importance before starting treatment. Treatment of pars planitis has been a controversial issue. There is no consensus specifically for treatment of cases with minimal inflammation and relatively good visual acuity. However, current experience shows that pars planitis may cause severe inflammation and needs an aggressive treatment. A stepladder approach including corticosteroids, immunosupressive agents, anti-tumor necrosis factor-alpha and pars plana vitrectomy and/or laser photocoagulation is the most commonly used method for treatment of pars planitis. Adequate control of inflammation and prompt detection of associated complications are crucial in order to improve the overall prognosis of the disease. PMID:27051493

  1. Comparison of the effects of PAR1 antagonists, PAR4 antagonists, and their combinations on thrombin-induced human platelet activation.

    PubMed

    Wu, Chin-Chung; Teng, Che-Ming

    2006-09-28

    Thrombin activates human platelets through proteolytic activation of two protease-activated receptors (PARs), PAR1 and PAR4. In the present study, we show that, RWJ-56110, a potent synthetic PAR1 antagonist, inhibited platelet aggregation caused by a low concentration (0.05 U/ml) of thrombin, but lost its effectiveness when higher concentrations of thrombin were used as stimulators. YD-3, a non-peptide PAR4 antagonist, alone had little or no effect on thrombin-induced platelet aggregation, significantly enhanced the anti-aggregatory activity of PAR1 antagonist. In addition, we demonstrate for the first time that P-selectin expression in thrombin-stimulated platelets can be synergistically prevented by combined treatment of PAR1 antagonist and PAR4 antagonist. These results indicate that thrombin-induced platelet activation cannot be effectively inhibited by just blocking either single thrombin receptor pathway, and suggest a rationale for potential combination therapy in arterial thrombosis. PMID:16890935

  2. Regulation of protease-activated receptor (PAR) 1 and PAR4 signaling in human platelets by compartmentalized cyclic nucleotide actions.

    PubMed

    Bilodeau, Matthew L; Hamm, Heidi E

    2007-08-01

    Thrombin potently regulates human platelets by the G protein-coupled receptors protease-activated receptor (PAR) 1 and PAR4. Platelet activation by thrombin and other agonists is broadly inhibited by prostacyclin and nitric oxide acting through adenylyl and guanylyl cyclases to elevate cAMP and cGMP levels, respectively. Using forskolin and YC-1 [3-(5'-hydroxymethyl-2'-furyl)-1-benzylindazole] to selectively activate the adenylyl and guanylyl cyclases, respectively, and the membrane-permeable analogs N(6),2'-O-dibutyryladenosine-3'-5'-cAMP (dibutyryl-cAMP) and 8-(4-parachlorophenylthoi)-cGMP (8-pCPT-cGMP), we sought to identify key antiplatelet steps for cyclic nucleotide actions in blocking platelet activation by PAR1 versus PAR4. Platelet aggregation by PAR1 or PAR4 was inhibited with similar EC(50) of 1.2 to 2.1 microM forskolin, 31 to 33 microM YC-1, 57 to 150 microM dibutyryl-cAMP, and 220 to 410 microM 8-pCPT-cGMP. There was a marked left shift in the inhibitory potencies of forskolin and YC-1 for alpha-granule release and glycoprotein IIbIIIa/integrin alphaIIbbeta3 activation (i.e., EC(50) of 1-60 and 40-1300 nM, respectively) that was not observed for dibutyryl-cAMP and 8-pCPT-cGMP (i.e., EC(50) of 200-600 and 40-140 microM, respectively). This inhibition was essentially instantaneous, and measurements of cyclic nucleotide levels and kinase activities support a model of compartmentation involving the cyclic nucleotide effectors and regulators and the key molecular targets for this platelet inhibition. The different sensitivities of PAR1 and PAR4 to inhibition of calcium mobilization and dense granule release identify key antiplatelet steps for cyclic nucleotide actions and are consistent with the signaling models for these receptors. Specifically, PAR4 inhibition depends on the regulation of both calcium mobilization and dense granule release, and PAR1 inhibition depends predominantly on the regulation of dense granule release. PMID:17525299

  3. Stochastic Self-Assembly of ParB Proteins Builds the Bacterial DNA Segregation Apparatus.

    PubMed

    Sanchez, Aurore; Cattoni, Diego I; Walter, Jean-Charles; Rech, Jérôme; Parmeggiani, Andrea; Nollmann, Marcelo; Bouet, Jean-Yves

    2015-08-26

    Many canonical processes in molecular biology rely on the dynamic assembly of higher-order nucleoprotein complexes. In bacteria, the assembly mechanism of ParABS, the nucleoprotein super-complex that actively segregates the bacterial chromosome and many plasmids, remains elusive. We combined super-resolution microscopy, quantitative genome-wide surveys, biochemistry, and mathematical modeling to investigate the assembly of ParB at the centromere-like sequences parS. We found that nearly all ParB molecules are actively confined around parS by a network of synergistic protein-protein and protein-DNA interactions. Interrogation of the empirically determined, high-resolution ParB genomic distribution with modeling suggests that instead of binding only to specific sequences and subsequently spreading, ParB binds stochastically around parS over long distances. We propose a new model for the formation of the ParABS partition complex based on nucleation and caging: ParB forms a dynamic lattice with the DNA around parS. This assembly model and approach to characterizing large-scale, dynamic interactions between macromolecules may be generalizable to many unrelated machineries that self-assemble in superstructures. PMID:27135801

  4. An investigation of the relationships between rate and driving force in simple uncatalysed and enzyme-catalysed reactions with applications of the findings to chemiosmotic reactions.

    PubMed Central

    Stoner, C D

    1992-01-01

    Both the rate and the driving force of a reaction can be expressed in terms of the concentrations of the reactants and products. Consequently, rate and driving force can be expressed as a function of each other. This has been done for a single-reactant, single-product, uncatalysed reaction and its enzyme-catalysed equivalent using the van't Hoff reaction isotherm and Haldane's generalized Michaelis-Menten rate equation, the primary objective being explanation of the exponential and sigmoidal relationships between reaction rate and delta mu H+ commonly observed in studies on chemiosmotic reactions. Acquisition of a purely thermodynamic rate vs. driving-force relationship requires recognition of the intensive and extensive variables and maintenance of the extensive variables constant. This relationship is identical for the two reactions and is hyperbolic or sigmoidal, depending on whether the equilibrium constant is smaller or larger than unity. In the case of the catalysed reaction, acquisition of the purely thermodynamic relationship requires the assumption that the enzyme be equally effective in catalysing the forward and backward reactions. If this condition is not met, the relationship is modified by the enzyme in a manner which can be determined from the ratio of the Michaelis constants of the reactant and product. Under conditions of enzyme saturation in respect to reactant+product, the rate vs. driving-force relationship is determined exclusively by the thermodynamics of the reaction and a single kinetic parameter, the magnitude of which is determined by the relative effectiveness of the enzyme in catalysing the forward and backward reactions. In view of this finding, it is pointed out that, since the catalytic components of chemiosmotic reactions appear to be saturated with respect to the reactant-product pair that is varied in experimental rate vs. delta mu H+ determinations, and that, since many complex enzymic reactions conform to the simple Michaelis

  5. Par Pond vegetation status Summer 1995 -- September survey descriptive summary

    SciTech Connect

    Mackey, H.E. Jr.; Riley, R.S.

    1995-09-01

    The water level of Par Pond was lowered approximately 20 feet in mid-1991 in order to protect downstream residents from possible dam failure suggested by subsidence on the downstream slope of the dam and to repair the dam. This lowering exposed both emergent and nonemergent macrophyte beds to drying conditions resulting in extensive losses. A survey of the emergent shoreline aquatic plant communities began in June 1995, three months after the refilling of Par Pond to approximately 200 feet above mean sea level and continued with this mid-September survey. Communities similar to the pre-drawdown Par Pond aquatic plant communities are becoming re-established; especially, beds of maidencane, lotus, waterlily, and watershield are now extensive and well established. Cattail occurrence continues to increase, but large beds common to Par Pond prior to the drawdown have not formed. Future surveys during the late growing seasons of 1995, and throughout 1996 and 1997, along with the evaluation of satellite data to map the areal extent of the macrophyte beds of Par Pond, are planned.

  6. Par Pond vegetation status Summer 1995 -- October survey descriptive summary

    SciTech Connect

    Mackey, H.E. Jr.; Riley, R.S.

    1995-11-01

    The water level of Par Pond was lowered approximately 20 feet in mid-1991 in order to protect downstream residents from possible dam failure suggested by subsidence on the downstream slope of the dam and to repair the dam. This lowering exposed both emergent and nonemergent macrophyte beds to drying conditions resulting in extensive losses. A survey of the emergent shoreline aquatic plant communities began in June 1995, three months after the refilling of Par Pond to approximately 200 feet above mean sea level and continued with this late October survey. Communities similar to the pre-drawdown Par Pond aquatic plant communities are becoming re-established; especially, beds of maiden cane, lotus, waterlily, and watershield are now extensive and well established. Cattail occurrence continues to increase, but large beds common to Par Pond prior to the drawdown have not formed. Future surveys throughout 1996 and 1997, along with the continued evaluation of satellite data to map the areal extent of the macrophyte beds of Par Pond, are planned.

  7. [Plan for the Elimination of Measles and Rubella in Spain].

    PubMed

    Limia Sánchez, Aurora

    2015-01-01

    The current Plan for the elimination of measles and rubella is made of the Plan for the elimination of measles in Spain, set up in 2001, and the Surveillance protocol of rubella and congenital rubella syndrome in the phase of elimination, established in 2007. The monitoring of the elimination of both diseases conducted from the European Region of World Health Organization (WHO) has been reinforced since 2010. An annual report with information on the situation of measles and rubella in The Member Estates is being requested since 2013. The Ministry of Health, Social Services and Equality nominated a National Committee for Verification of Measles and Rubella Elimination in 2013, for the review and delivery of the requested information. The strategies and activities currently recommended from the WHO European Region, the verification process in Spain, and the steps to follow for the updating of the Plan for the elimination of measles and rubella in Spain are mentioned in this article.

  8. Bubble Eliminator Based on Centrifugal Flow

    NASA Technical Reports Server (NTRS)

    Gonda, Steve R.; Tsao, Yow-Min D.; Lee, Wenshan

    2004-01-01

    The fluid bubble eliminator (FBE) is a device that removes gas bubbles from a flowing liquid. The FBE contains no moving parts and does not require any power input beyond that needed to pump the liquid. In the FBE, the buoyant force for separating the gas from the liquid is provided by a radial pressure gradient associated with a centrifugal flow of the liquid and any entrained bubbles. A device based on a similar principle is described in Centrifugal Adsorption Cartridge System (MSC- 22863), which appears on page 48 of this issue. The FBE was originally intended for use in filtering bubbles out of a liquid flowing relatively slowly in a bioreactor system in microgravity. Versions that operate in normal Earth gravitation at greater flow speeds may also be feasible. The FBE (see figure) is constructed as a cartridge that includes two concentric cylinders with flanges at the ends. The outer cylinder is an impermeable housing; the inner cylinder comprises a gas-permeable, liquid-impermeable membrane covering a perforated inner tube. Multiple spiral disks that collectively constitute a spiral ramp are mounted in the space between the inner and outer cylinders. The liquid enters the FBE through an end flange, flows in the annular space between the cylinders, and leaves through the opposite end flange. The spiral disks channel the liquid into a spiral flow, the circumferential component of which gives rise to the desired centrifugal effect. The resulting radial pressure gradient forces the bubbles radially inward; that is, toward the inner cylinder. At the inner cylinder, the gas-permeable, liquid-impermeable membrane allows the bubbles to enter the perforated inner tube while keeping the liquid in the space between the inner and outer cylinders. The gas thus collected can be vented via an endflange connection to the inner tube. The centripetal acceleration (and thus the radial pressure gradient) is approximately proportional to the square of the flow speed and

  9. Reduced Switching Frequency Active Harmonic Elimination for Multilevel Converters

    SciTech Connect

    Du, Zhong; Tolbert, Leon M; Chiasson, John N; Ozpineci, Burak

    2008-01-01

    This paper presents a reduced switching-frequency active-harmonic-elimination method (RAHEM) to eliminate any number of specific order harmonics of multilevel converters. First, resultant theory is applied to transcendental equations to eliminate low-order harmonics and to determine switching angles for a fundamental frequency-switching scheme. Next, based on the number of harmonics to be eliminated, Newton climbing method is applied to transcendental equations to eliminate high-order harmonics and to determine switching angles for the fundamental frequency-switching scheme. Third, the magnitudes and phases of the residual lower order harmonics are computed, generated, and subtracted from the original voltage waveform to eliminate these low-order harmonics. Compared to the active-harmonic-elimination method (AHEM), which generates square waves to cancel high-order harmonics, RAHEM has lower switching frequency. The simulation results show that the method can effectively eliminate all the specific harmonics, and a low total harmonic distortion (THD) near sine wave is produced. An experimental 11-level H-bridge multilevel converter with a field-programmable gate-array controller is employed to experimentally validate the method. The experimental results show that RAHEM does effectively eliminate any number of specific harmonics, and the output voltage waveform has low switching frequency and low THD.

  10. Variable-capacitance tachometer eliminates troublesome magnetic fields

    NASA Technical Reports Server (NTRS)

    1966-01-01

    Dual variable-capacitance tachometer measures angular speed and sense of rotation without magnetic components. Thus it eliminates magnetic flux interference with associated instrumentation in an electromechanical system.

  11. PAR-1 phosphorylates Mind bomb to promote vertebrate neurogenesis

    PubMed Central

    Ossipova, Olga; Ezan, Jerome; Sokol, Sergei Y.

    2010-01-01

    Summary Generation of neurons in the vertebrate central nervous system requires complex transcriptional regulatory network and signaling processes in polarized neuroepithelial progenitor cells. Here we demonstrate that neurogenesis in the Xenopus neural plate in vivo and mammalian neural progenitors in vitro involves intrinsic antagonistic activities of the polarity proteins PAR-1 and aPKC. Furthermore, we show that Mind bomb (Mib), a ubiquitin ligase that promotes Notch ligand trafficking and activity, is a crucial molecular substrate for PAR-1. The phosphorylation of Mib by PAR-1 results in Mib degradation, repression of Notch signaling and stimulation of neuronal differentiation. These observations suggest a conserved mechanism for neuronal fate determination that might operate during asymmetric divisions of polarized neural progenitor cells. PMID:19686683

  12. Experimental and theoretical insights into the oxodiperoxomolybdenum-catalysed sulphide oxidation using hydrogen peroxide in ionic liquids.

    PubMed

    Carrasco, Carlos J; Montilla, Francisco; Alvarez, Eleuterio; Mealli, Carlo; Manca, Gabriele; Galindo, Agustín

    2014-09-28

    The oxidation of organic sulphides with aqueous hydrogen peroxide in ionic liquids (ILs) catalysed by oxodiperoxomolybdenum complexes was investigated. The selective formation of several sulfones was achieved using the 1 : 3 ratio of sulphide : H2O2 in [C4mim][PF6] (C4mim = 1-butyl-3-methylimidazolium) in a reaction catalysed by the [Mo(O)(O2)2(H2O)n] complex. Conversely, sulfoxides were produced with good selectivities using a 1 : 1 ratio in the same solvent in a 1 h reaction with [Mo(O)(O2)2(Mepz)2] (Mepz = methylpyrazol). The use of [C4mim][PF6] as the solvent was advantageous for two reasons: (i) the improved performance of the H2O2-IL combination; (ii) recycling of the catalyst/IL mixture without a significant diminution of conversion or selectivity. A DFT analysis using the [Mo(O)(O2)2(L)] catalysts (L = Mepz, a; 3,5-dimethylpyrazole, dmpz, b; and H2O, c) indicated that a Sharpless-type outer-sphere mechanism is more probable than a Thiel-type one. The highest barrier of the catalytic profile was the oxo-transfer step, in which the nucleophilic attack of sulphide onto the peroxide ligand occurred with formation of dioxoperoxo species. In order to yield the sulfoxide and the starting catalyst, the oxidation of the resulting dioxoperoxo species with H2O2 was found to be the most favourable pathway. Subsequently, the sulfoxide to sulfone oxidation was performed through a similar mechanism involving the [Mo(O)(O2)2(L)] catalyst. The comparable energies found for the successive two oxo-transfer steps were in agreement with the experimental formation of sulfone in both the reaction with an excess of the oxidant and the stoichiometric reaction in the absence of the oxidant. In the latter case, diphenylsulfone was isolated as the major product in the 1 : 1 combination of diphenylsulphide and [Mo(O)(O2)2(Mepz)2] in the ionic liquid [C4mim][PF6]. Also, the compounds [HMepz]4[Mo8O26(Mepz)2]·2H2O, 1, [Hdmpz]4[Mo8O26(dmpz)2]·2dmpz, , and [Hpz]4[Mo8O22(O2

  13. Implementation of steady state approximation for modelling of reaction kinetic of UV catalysed hydrogen peroxide oxidation of starch

    NASA Astrophysics Data System (ADS)

    Kumoro, Andri Cahyo; Retnowati, Diah Susetyo; Ratnawati, Budiyati, Catarina Sri

    2015-12-01

    With regard to its low viscosity, high stability, clarity, film forming and binding properties, oxidised starch has been widely used in various applications specifically in the food, paper, textile, laundry finishing and binding materials industries. A number of methods have been used to produce oxidised starch through reactions with various oxidizing agents, such as hydrogen peroxide, air oxygen, ozone, bromine, chromic acid, permanganate, nitrogen dioxide and hypochlorite. Unfortunately, most of previous works reported in the literatures were focused on the study of reaction mechanism and physicochemical properties characterization of the oxidised starches produced without investigation of the reaction kinetics of the oxidation process. This work aimed to develop a simple kinetic model for UV catalysed hydrogen peroxide oxidation of starch through implementation of steady state approximation for the radical reaction rates. The model was then verified using experimental data available in the literature. The model verification revealed that the proposed model shows its good agreement with the experimental data as indicated by an average absolute relative error of only 2.45%. The model also confirmed that carboxyl groups are oxidised further by hydroxyl radical. The carbonyl production rate was found to follow first order reaction with respect to carbonyl concentration. Similarly, carboxyl production rate also followed first order reaction with respect to carbonyl concentration. The apparent reaction rate constant for carbonyl formation and oxidation were 6.24 × 104 s-1 and 1.01 × 104 M-1.s-1, respectively. While apparent reaction rate constant for carboxyl oxidation was 4.86 × 104 M-1.s-1.

  14. Catalytic and substrate promiscuity: distinct multiple chemistries catalysed by the phosphatase domain of receptor protein tyrosine phosphatase.

    PubMed

    Srinivasan, Bharath; Marks, Hanna; Mitra, Sreyoshi; Smalley, David M; Skolnick, Jeffrey

    2016-07-15

    The presence of latent activities in enzymes is posited to underlie the natural evolution of new catalytic functions. However, the prevalence and extent of such substrate and catalytic ambiguity in evolved enzymes is difficult to address experimentally given the order-of-magnitude difference in the activities for native and, sometimes, promiscuous substrate/s. Further, such latent functions are of special interest when the activities concerned do not fall into the domain of substrate promiscuity. In the present study, we show a special case of such latent enzyme activity by demonstrating the presence of two mechanistically distinct reactions catalysed by the catalytic domain of receptor protein tyrosine phosphatase isoform δ (PTPRδ). The primary catalytic activity involves the hydrolysis of a phosphomonoester bond (C─O─P) with high catalytic efficiency, whereas the secondary activity is the hydrolysis of a glycosidic bond (C─O─C) with poorer catalytic efficiency. This enzyme also displays substrate promiscuity by hydrolysing diester bonds while being highly discriminative for its monoester substrates. To confirm these activities, we also demonstrated their presence on the catalytic domain of protein tyrosine phosphatase Ω (PTPRΩ), a homologue of PTPRδ. Studies on the rate, metal-ion dependence, pH dependence and inhibition of the respective activities showed that they are markedly different. This is the first study that demonstrates a novel sugar hydrolase and diesterase activity for the phosphatase domain (PD) of PTPRδ and PTPRΩ. This work has significant implications for both understanding the evolution of enzymatic activity and the possible physiological role of this new chemistry. Our findings suggest that the genome might harbour a wealth of such alternative latent enzyme activities in the same protein domain that renders our knowledge of metabolic networks incomplete.

  15. Hierarchically structured meso-macroporous aluminosilicates with high tetrahedral aluminium content in acid catalysed esterification of fatty acids.

    PubMed

    Lemaire, Arnaud; Wang, Quan-Yi; Wei, Yingxu; Liu, Zhongmin; Su, Bao-Lian

    2011-11-15

    A simple synthesis pathway has been developed for the design of hierarchically structured spongy or spherical voids assembled meso-macroporous aluminosilicates with high tetrahedral aluminium content on the basis of the aqueous polymerisation of new stabilized alkoxy-bridged single molecular precursors. The intimate mixing of an aluminosilicate ester (sec-BuO)(2)-Al-O-Si(OEt)(3) and a silica co-reactant (tetramethoxysilane, TMOS) with variable ratios and the use of alkaline solutions (pH 13.0 and 13.5) improve significantly the heterocondensation rates between the highly reactive aluminium alkoxide part of the single precursor and added silica co-reactant, leading to aluminosilicate materials with high intra-framework aluminium content and low Si/Al ratios. The spherically-shaped meso-macroporosity was spontaneously generated by the release of high amount of liquid by-products (water/alcohol molecules) produced during the rapid hydrolysis and condensation processes of this double alkoxide and the TMOS co-reactant. It has been observed that both pH value and Al-Si/TMOS molar ratio can strongly affect the macroporous structure formation. Increasing pH value, even slightly from 13 to 13.5, can significantly favour the incorporation of Al atoms in tetrahedral position of the framework. After the total ionic exchange of Na(+) compensating cations, catalytic tests of obtained materials were realised in the esterification reaction of high free fatty acid (FFA) oils, showing their higher catalytic activity compared to commercial Bentonite clay, and their potential applications as catalyst supports in acid catalysed reactions.

  16. The Oxidative State of LDL is the Major Determinant of Anti/Prooxidant Effect of Coffee on Cu Catalysed Peroxidation.

    PubMed

    Carru, Ciriaco; Pasciu, Valeria; Sotgia, Salvatore; Zinellu, Angelo; Nicoli, Maria Cristina; Deiana, Luca; Tadolini, Bruna; Sanna, Bastiano; Masala, Bruno; Pintus, Gianfranco

    2011-01-01

    Antioxidants exert contrasting effect on low density lipoprotein (LDL) oxidation catalysed by metals, acting as pro-oxidants under select in vitro conditions. Through our study on the effect of coffee on LDL oxidation, we identified the parameters governing this phenomenon, contributing to the comprehension of its mechanism and discovering significant implications for correct alimentary recommendations. By measuring conjugated diene formation, we have analysed the quantitative and qualitative effects exerted by an extract of roasted coffee on LDL oxidation triggered by copper sulphate. When the relative effects of different coffee concentrations were plotted against the lag time (LT) of control LDL (C-LDL), the apparently random experimental data arranged in sensible patterns: by increasing the LT the antioxidant activity of coffee decreased progressively to become prooxidant. The critical LT, at which coffee switches from antioxidant to prooxidant, increased by increasing coffee concentration. Also the contrasting results obtained following a delayed addition of coffee to the assay, arranged in a simple pattern when referred to the LT of C-LDL: the prooxidant effect decreased to become antioxidant as the LT of C-LDL increased. The dependence of coffee effect on the LT of C-LDL was influenced by LDL but not by metal catalyst concentration. These novel findings point to the oxidative state of LDL as a major parameter controlling the anti/prooxidant effect of coffee and suggest the LT of C-LDL as a potent analytical tool to express experimental data when studying the action exerted by a compound on LDL oxidation. PMID:21633665

  17. 3 CFR - Implementing the Prison Rape Elimination Act

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ... 3 The President 1 2013-01-01 2013-01-01 false Implementing the Prison Rape Elimination Act Presidential Documents Other Presidential Documents Memorandum of May 17, 2012 Implementing the Prison Rape... victim, is an assault on human dignity and an affront to American values. The Prison Rape Elimination...

  18. Making Career Decisions--A Sequential Elimination Approach.

    ERIC Educational Resources Information Center

    Gati, Itamar

    1986-01-01

    Presents a model for career decision making based on the sequential elimination of occupational alternatives, an adaptation for career decisions of Tversky's (1972) elimination-by-aspects theory of choice. The expected utility approach is reviewed as a representative compensatory model for career decisions. Advantages, disadvantages, and…

  19. 10 CFR 63.23 - Elimination of repetition.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... 10 Energy 2 2010-01-01 2010-01-01 false Elimination of repetition. 63.23 Section 63.23 Energy NUCLEAR REGULATORY COMMISSION (CONTINUED) DISPOSAL OF HIGH-LEVEL RADIOACTIVE WASTES IN A GEOLOGIC REPOSITORY AT YUCCA MOUNTAIN, NEVADA Licenses License Application § 63.23 Elimination of repetition. In...

  20. 10 CFR 63.23 - Elimination of repetition.

    Code of Federal Regulations, 2012 CFR

    2012-01-01

    ... 10 Energy 2 2012-01-01 2012-01-01 false Elimination of repetition. 63.23 Section 63.23 Energy NUCLEAR REGULATORY COMMISSION (CONTINUED) DISPOSAL OF HIGH-LEVEL RADIOACTIVE WASTES IN A GEOLOGIC REPOSITORY AT YUCCA MOUNTAIN, NEVADA Licenses License Application § 63.23 Elimination of repetition. In...

  1. 10 CFR 63.23 - Elimination of repetition.

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ... 10 Energy 2 2013-01-01 2013-01-01 false Elimination of repetition. 63.23 Section 63.23 Energy NUCLEAR REGULATORY COMMISSION (CONTINUED) DISPOSAL OF HIGH-LEVEL RADIOACTIVE WASTES IN A GEOLOGIC REPOSITORY AT YUCCA MOUNTAIN, NEVADA Licenses License Application § 63.23 Elimination of repetition. In...

  2. 10 CFR 63.23 - Elimination of repetition.

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ... 10 Energy 2 2011-01-01 2011-01-01 false Elimination of repetition. 63.23 Section 63.23 Energy NUCLEAR REGULATORY COMMISSION (CONTINUED) DISPOSAL OF HIGH-LEVEL RADIOACTIVE WASTES IN A GEOLOGIC REPOSITORY AT YUCCA MOUNTAIN, NEVADA Licenses License Application § 63.23 Elimination of repetition. In...

  3. 10 CFR 63.23 - Elimination of repetition.

    Code of Federal Regulations, 2014 CFR

    2014-01-01

    ... 10 Energy 2 2014-01-01 2014-01-01 false Elimination of repetition. 63.23 Section 63.23 Energy NUCLEAR REGULATORY COMMISSION (CONTINUED) DISPOSAL OF HIGH-LEVEL RADIOACTIVE WASTES IN A GEOLOGIC REPOSITORY AT YUCCA MOUNTAIN, NEVADA Licenses License Application § 63.23 Elimination of repetition. In...

  4. 10 CFR 61.21 - Elimination of repetition.

    Code of Federal Regulations, 2012 CFR

    2012-01-01

    ... 10 Energy 2 2012-01-01 2012-01-01 false Elimination of repetition. 61.21 Section 61.21 Energy NUCLEAR REGULATORY COMMISSION (CONTINUED) LICENSING REQUIREMENTS FOR LAND DISPOSAL OF RADIOACTIVE WASTE Licenses § 61.21 Elimination of repetition. In its application, the applicant may incorporate by...

  5. 10 CFR 60.23 - Elimination of repetition.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... 10 Energy 2 2010-01-01 2010-01-01 false Elimination of repetition. 60.23 Section 60.23 Energy NUCLEAR REGULATORY COMMISSION (CONTINUED) DISPOSAL OF HIGH-LEVEL RADIOACTIVE WASTES IN GEOLOGIC REPOSITORIES Licenses License Applications § 60.23 Elimination of repetition. In its application,...

  6. 10 CFR 60.23 - Elimination of repetition.

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ... 10 Energy 2 2011-01-01 2011-01-01 false Elimination of repetition. 60.23 Section 60.23 Energy NUCLEAR REGULATORY COMMISSION (CONTINUED) DISPOSAL OF HIGH-LEVEL RADIOACTIVE WASTES IN GEOLOGIC REPOSITORIES Licenses License Applications § 60.23 Elimination of repetition. In its application,...

  7. 10 CFR 60.23 - Elimination of repetition.

    Code of Federal Regulations, 2014 CFR

    2014-01-01

    ... 10 Energy 2 2014-01-01 2014-01-01 false Elimination of repetition. 60.23 Section 60.23 Energy NUCLEAR REGULATORY COMMISSION (CONTINUED) DISPOSAL OF HIGH-LEVEL RADIOACTIVE WASTES IN GEOLOGIC REPOSITORIES Licenses License Applications § 60.23 Elimination of repetition. In its application,...

  8. 10 CFR 60.23 - Elimination of repetition.

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ... 10 Energy 2 2013-01-01 2013-01-01 false Elimination of repetition. 60.23 Section 60.23 Energy NUCLEAR REGULATORY COMMISSION (CONTINUED) DISPOSAL OF HIGH-LEVEL RADIOACTIVE WASTES IN GEOLOGIC REPOSITORIES Licenses License Applications § 60.23 Elimination of repetition. In its application,...

  9. 10 CFR 60.23 - Elimination of repetition.

    Code of Federal Regulations, 2012 CFR

    2012-01-01

    ... 10 Energy 2 2012-01-01 2012-01-01 false Elimination of repetition. 60.23 Section 60.23 Energy NUCLEAR REGULATORY COMMISSION (CONTINUED) DISPOSAL OF HIGH-LEVEL RADIOACTIVE WASTES IN GEOLOGIC REPOSITORIES Licenses License Applications § 60.23 Elimination of repetition. In its application,...

  10. 10 CFR 61.21 - Elimination of repetition.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... 10 Energy 2 2010-01-01 2010-01-01 false Elimination of repetition. 61.21 Section 61.21 Energy NUCLEAR REGULATORY COMMISSION (CONTINUED) LICENSING REQUIREMENTS FOR LAND DISPOSAL OF RADIOACTIVE WASTE Licenses § 61.21 Elimination of repetition. In its application, the applicant may incorporate by...

  11. 10 CFR 61.21 - Elimination of repetition.

    Code of Federal Regulations, 2014 CFR

    2014-01-01

    ... 10 Energy 2 2014-01-01 2014-01-01 false Elimination of repetition. 61.21 Section 61.21 Energy NUCLEAR REGULATORY COMMISSION (CONTINUED) LICENSING REQUIREMENTS FOR LAND DISPOSAL OF RADIOACTIVE WASTE Licenses § 61.21 Elimination of repetition. In its application, the applicant may incorporate by...

  12. 10 CFR 61.21 - Elimination of repetition.

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ... 10 Energy 2 2013-01-01 2013-01-01 false Elimination of repetition. 61.21 Section 61.21 Energy NUCLEAR REGULATORY COMMISSION (CONTINUED) LICENSING REQUIREMENTS FOR LAND DISPOSAL OF RADIOACTIVE WASTE Licenses § 61.21 Elimination of repetition. In its application, the applicant may incorporate by...

  13. 10 CFR 61.21 - Elimination of repetition.

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ... 10 Energy 2 2011-01-01 2011-01-01 false Elimination of repetition. 61.21 Section 61.21 Energy NUCLEAR REGULATORY COMMISSION (CONTINUED) LICENSING REQUIREMENTS FOR LAND DISPOSAL OF RADIOACTIVE WASTE Licenses § 61.21 Elimination of repetition. In its application, the applicant may incorporate by...

  14. Gains and Pitfalls of Quantifier Elimination as a Teaching Tool

    ERIC Educational Resources Information Center

    Oldenburg, Reinhard

    2015-01-01

    Quantifier Elimination is a procedure that allows simplification of logical formulas that contain quantifiers. Many mathematical concepts are defined in terms of quantifiers and especially in calculus their use has been identified as an obstacle in the learning process. The automatic deduction provided by quantifier elimination thus allows…

  15. 10 CFR 52.8 - Combining licenses; elimination of repetition.

    Code of Federal Regulations, 2014 CFR

    2014-01-01

    ... 10 Energy 2 2014-01-01 2014-01-01 false Combining licenses; elimination of repetition. 52.8 Section 52.8 Energy NUCLEAR REGULATORY COMMISSION (CONTINUED) LICENSES, CERTIFICATIONS, AND APPROVALS FOR NUCLEAR POWER PLANTS General Provisions § 52.8 Combining licenses; elimination of repetition. (a)...

  16. 10 CFR 52.8 - Combining licenses; elimination of repetition.

    Code of Federal Regulations, 2012 CFR

    2012-01-01

    ... 10 Energy 2 2012-01-01 2012-01-01 false Combining licenses; elimination of repetition. 52.8 Section 52.8 Energy NUCLEAR REGULATORY COMMISSION (CONTINUED) LICENSES, CERTIFICATIONS, AND APPROVALS FOR NUCLEAR POWER PLANTS General Provisions § 52.8 Combining licenses; elimination of repetition. (a)...

  17. 10 CFR 52.8 - Combining licenses; elimination of repetition.

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ... 10 Energy 2 2013-01-01 2013-01-01 false Combining licenses; elimination of repetition. 52.8 Section 52.8 Energy NUCLEAR REGULATORY COMMISSION (CONTINUED) LICENSES, CERTIFICATIONS, AND APPROVALS FOR NUCLEAR POWER PLANTS General Provisions § 52.8 Combining licenses; elimination of repetition. (a)...

  18. 10 CFR 52.8 - Combining licenses; elimination of repetition.

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ... 10 Energy 2 2011-01-01 2011-01-01 false Combining licenses; elimination of repetition. 52.8 Section 52.8 Energy NUCLEAR REGULATORY COMMISSION (CONTINUED) LICENSES, CERTIFICATIONS, AND APPROVALS FOR NUCLEAR POWER PLANTS General Provisions § 52.8 Combining licenses; elimination of repetition. (a)...

  19. 10 CFR 52.8 - Combining licenses; elimination of repetition.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... 10 Energy 2 2010-01-01 2010-01-01 false Combining licenses; elimination of repetition. 52.8 Section 52.8 Energy NUCLEAR REGULATORY COMMISSION (CONTINUED) LICENSES, CERTIFICATIONS, AND APPROVALS FOR NUCLEAR POWER PLANTS General Provisions § 52.8 Combining licenses; elimination of repetition. (a)...

  20. Estimation of Half-Life for Single Compartmental Elimination Models

    ERIC Educational Resources Information Center

    Mickens, R. E.; Rucker, S.

    2008-01-01

    A method is presented to calculate accurate approximations to the half-life values of elimination systems modelled by one compartment. The major advantage of this method is that only algebraic mathematical operations are required. The results will be of value not only to students beginning the study of elimination kinetics, but also to…

  1. Par Pond vegetation status summer 1995 - July survey descriptive summary

    SciTech Connect

    Mackey, H.E. Jr.; Riley, R.S.

    1995-07-01

    A survey of the emergent shoreline aquatic plant, communities began in June 1995, three months after the refilling of Par Pond to approximately 200 feet (61 meters) above mean sea level, and continued with this July survey. Aquatic plant communities, similar to the pre-drawdown Par Pond communities, are becoming reestablished. Beds of maidencane (Panicum hemitomon), lotus (Nelumbo lutea), water lily (Nymphaea odorata), and watershield (Brasenia schreberi) are now extensive and well established. In addition, within isolated coves, extensive beds of water lilies and spike-rush (Eleocharis sp.) are common. Cattail occurrence has increased since refill, but large beds common to Par Pond prior to the drawdown have not formed. Invasion of willow (Salix sp.) and red maple (Acer rubrum) occurred along the lake shoreline during drawdown. The red maples along the present shoreline are beginning to show evidence of stress and mortality from flooding over the past four months. Some of the willows appear to be stressed as well. The loblolly pines (Pinus taeda), which were flooded in all but the shallow shoreline areas, are now dead. Future surveys are planned for the growing seasons of 1995, 1996, and 1997, along with the evaluation of satellite data for mapping the areal extent of the macrophyte beds of Par Pond.

  2. The Pars Triangularis in Dyslexia and ADHD: A Comprehensive Approach

    ERIC Educational Resources Information Center

    Kibby, Michelle Y.; Kroese, Judith M.; Krebbs, Hillery; Hill, Crystal E.; Hynd, George W.

    2009-01-01

    Limited research has been conducted on the structure of the pars triangularis (PT) in dyslexia despite functional neuroimaging research finding it may play a role in phonological processing. Furthermore, research to date has not examined PT size in ADHD even though the right inferior frontal region has been implicated in the disorder. Hence, one…

  3. Aqueous misdirection following pars plana vitrectomy and silicone oil injection

    PubMed Central

    Ghoraba, Hammouda H; Ghali, Ali Ahmed; Mansour, Hosam Othman

    2015-01-01

    Purpose To report a retrospective series of seven phakic eyes of seven patients suffering from a malignant glaucoma-like syndrome following pars plana vitrectomy and silicone oil (SO) injection. Materials and methods Seven eyes with retinal detachment treated with pars plana vitrectomy with or without scleral buckling with SO tamponade. This was followed by cataract extraction to manage the elevated intraocular pressure (IOP). Results This was a retrospective review of seven cases that received pars plana vitrectomy and SO with or without scleral buckling for different causes of retinal detachment (three were rhegmatogenous and four were tractional). After a period ranging from 1 week to 1 month, they presented with malignant glaucoma-like manifestations; high IOP, shallow axial anterior chamber, and remarkable decrease of visual acuity. Atropine eye drops and anti-glaucoma medical treatment (topical and systemic) had been tried but failed to improve the condition. Dramatic decrease of IOP and deepening of the axial anterior chamber was observed in all cases in the first postoperative day after phacoemulsification and posterior chamber foldable intraocular lens implantation with posterior capsulotomy. Conclusion Aqueous misdirection syndrome may be observed following pars plana vitrectomy and SO tamponade. This must be differentiated from other causes of post vitrectomy glaucoma. Cataract extraction with posterior capsulotomy controls the condition. PMID:26056429

  4. Radiological impact of Par Pond drawdown from liquid effluent pathways

    SciTech Connect

    Carlton, W.H.; Hamby, D.M.

    1991-10-25

    The water level of Par Pond has been lowered over the past several months to reduce the effects in the event of catastrophic dam failure while assessing the condition of the dam and determining if repairs are necessary. In lowering the level of Par Pond, 60 billion liters of water containing low levels of tritium and cesium-137 were discharged to several onsite streams. SRS surface streams flow to the Savannah River. An assessment made to determine the total amount of tritium and Cs-137 discharged and to estimate the consequences to downstream Savannah River users. It is estimated that a total of 160 curies of tritium were displaced from Par Pond to the Savannah River between June 28, 1991 and September 19, 1991. This release could hypothetically result in a maximum individual dose of 3. 2{times}10{sup {minus}4} mrem and a total (80-km and drinking water populations) population dose of 1.4{times}10{sup {minus}2} person-rem. Likewise, a maximum individual dose of 5.0{times}10{sup {minus}2} mrem and a total population dose of 1.7{times}10{sup {minus}1} person- rem are predicted as a result of an estimated 0.21 curies of Cs-137 being discharged from Par Pond to the Savannah River.

  5. BOREAS RSS-10 TOMS Circumpolar One-Degree PAR Images

    NASA Technical Reports Server (NTRS)

    Dye, Dennis G.; Holben, Brent; Nickeson, Jaime (Editor); Hall, Forrest G. (Editor); Smith, David E. (Technical Monitor)

    2000-01-01

    The Boreal Ecosystem-Atmosphere Study (BOREAS) Remote Sensing Science (RSS)-10 team investigated the magnitude of daily, seasonal, and yearly variations of Photosynthetically Active Radiation (PAR) from ground and satellite observations. This data set contains satellite estimates of surface-incident PAR (400-700 nm, MJ/sq m) at one-degree spatial resolution. The spatial coverage is circumpolar from latitudes of 41 to 66 degrees north. The temporal coverage is from May through September for years 1979 through 1989. Eleven-year statistics are also provided: (1) mean, (2) standard deviation, and (3) coefficient of variation for 1979-89. The PAR estimates were derived from the global gridded ultraviolet reflectivity data product (average of 360, 380 nm) from the Nimbus-7 Total Ozone Mapping Spectrometer (TOMS). Image mask data are provided for identifying the boreal forest zone, and ocean/land and snow/ice-covered areas. The data are available as binary image format data files. The PAR data are available from the Earth Observing System Data and Information System (EOSDIS) Oak Ridge National Laboratory (ORNL) Distributed Active Archive Center (DAAC). The data files are available on a CD-ROM (see document number 20010000884).

  6. [Switzerland eliminates measles. National Strategy for the Elimination of Measles 2011-2015].

    PubMed

    Koch, D; Richard, J-L; Hanhart, J; Eckert, T; Eigenmann Schüttel, S

    2013-09-01

    The measles virus circulates within Switzerland in an endemic way leading to sporadic outbreaks. The most recent outbreak occurred in 2011. It lasted 9 months and had 687 reported cases. This is in contrast to 2012 when there were 66 cases,corresponding to an incidence of 8 cases per million inhabitants. During 2008-2010, the average national vaccination coverage for one or two doses of measles vaccine amounted to 92 and 83 % for 2-year-olds, 95 and 85 % for 8-year-olds, and 95 and 85 % for 16-year-olds, respectively. To improve the national vaccination coverage, the Federal Council adopted the National Strategy for the Elimination of Measles 2011-2015 in 2011.The strategy was drawn up in a participative process led by the Federal Office for Public Health.The cantons as key partners were represented by the Conference of the Cantonal Directors for Public Health and the Association of Cantonal Health Officers. The strategy pursues the vision of eliminating measles in Switzerland in order to protect the population against measles and its complications, including all persons who may not be vaccinated for medical reasons. The strategy comprises six axes of intervention:(1)political engagement and support by all stakeholders, (2)a targeted ≥ 95 % two-dose vaccination coverage for all 2-year-olds, (3)easier access and incentives for the booster vaccination for everyone in the 2-year-old age group up to those born in 1964, (4)communication and promotion, (5)uniform national outbreak control, and (6)targeted surveillance.

  7. Competing ParA structures space bacterial plasmids equally over the nucleoid.

    PubMed

    Ietswaart, Robert; Szardenings, Florian; Gerdes, Kenn; Howard, Martin

    2014-12-01

    Low copy number plasmids in bacteria require segregation for stable inheritance through cell division. This is often achieved by a parABC locus, comprising an ATPase ParA, DNA-binding protein ParB and a parC region, encoding ParB-binding sites. These minimal components space plasmids equally over the nucleoid, yet the underlying mechanism is not understood. Here we investigate a model where ParA-ATP can dynamically associate to the nucleoid and is hydrolyzed by plasmid-associated ParB, thereby creating nucleoid-bound, self-organizing ParA concentration gradients. We show mathematically that differences between competing ParA concentrations on either side of a plasmid can specify regular plasmid positioning. Such positioning can be achieved regardless of the exact mechanism of plasmid movement, including plasmid diffusion with ParA-mediated immobilization or directed plasmid motion induced by ParB/parC-stimulated ParA structure disassembly. However, we find experimentally that parABC from Escherichia coli plasmid pB171 increases plasmid mobility, inconsistent with diffusion/immobilization. Instead our observations favor directed plasmid motion. Our model predicts less oscillatory ParA dynamics than previously believed, a prediction we verify experimentally. We also show that ParA localization and plasmid positioning depend on the underlying nucleoid morphology, indicating that the chromosomal architecture constrains ParA structure formation. Our directed motion model unifies previously contradictory models for plasmid segregation and provides a robust mechanistic basis for self-organized plasmid spacing that may be widely applicable.

  8. ParA-mediated plasmid partition driven by protein pattern self-organization

    PubMed Central

    Hwang, Ling Chin; Vecchiarelli, Anthony G; Han, Yong-Woon; Mizuuchi, Michiyo; Harada, Yoshie; Funnell, Barbara E; Mizuuchi, Kiyoshi

    2013-01-01

    DNA segregation ensures the stable inheritance of genetic material prior to cell division. Many bacterial chromosomes and low-copy plasmids, such as the plasmids P1 and F, employ a three-component system to partition replicated genomes: a partition site on the DNA target, typically called parS, a partition site binding protein, typically called ParB, and a Walker-type ATPase, typically called ParA, which also binds non-specific DNA. In vivo, the ParA family of ATPases forms dynamic patterns over the nucleoid, but how ATP-driven patterning is involved in partition is unknown. We reconstituted and visualized ParA-mediated plasmid partition inside a DNA-carpeted flowcell, which acts as an artificial nucleoid. ParA and ParB transiently bridged plasmid to the DNA carpet. ParB-stimulated ATP hydrolysis by ParA resulted in ParA disassembly from the bridging complex and from the surrounding DNA carpet, which led to plasmid detachment. Our results support a diffusion-ratchet model, where ParB on the plasmid chases and redistributes the ParA gradient on the nucleoid, which in turn mobilizes the plasmid. PMID:23443047

  9. PH motifs in PAR1&2 endow breast cancer growth.

    PubMed

    Kancharla, A; Maoz, M; Jaber, M; Agranovich, D; Peretz, T; Grisaru-Granovsky, S; Uziely, B; Bar-Shavit, R

    2015-01-01

    Although emerging roles of protease-activated receptor1&2 (PAR1&2) in cancer are recognized, their underlying signalling events are poorly understood. Here we show signal-binding motifs in PAR1&2 that are critical for breast cancer growth. This occurs via the association of the pleckstrin homology (PH) domain with Akt/PKB as a key signalling event of PARs. Other PH-domain signal-proteins such as Etk/Bmx and Vav3 also associate with PAR1 and PAR2 through their PH domains. PAR1 and PAR2 bind with priority to Etk/Bmx. A point mutation in PAR2, H349A, but not in R352A, abrogates PH-protein association and is sufficient to markedly reduce PAR2-instigated breast tumour growth in vivo and placental extravillous trophoblast (EVT) invasion in vitro. Similarly, the PAR1 mutant hPar1-7A, which is unable to bind the PH domain, reduces mammary tumours and EVT invasion, endowing these motifs with physiological significance and underscoring the importance of these previously unknown PAR1 and PAR2 PH-domain-binding motifs in both pathological and physiological invasion processes. PMID:26600192

  10. PH motifs in PAR1&2 endow breast cancer growth

    PubMed Central

    Kancharla, A.; Maoz, M.; Jaber, M.; Agranovich, D.; Peretz, T.; Grisaru-Granovsky, S.; Uziely, B.; Bar-Shavit, R.

    2015-01-01

    Although emerging roles of protease-activated receptor1&2 (PAR1&2) in cancer are recognized, their underlying signalling events are poorly understood. Here we show signal-binding motifs in PAR1&2 that are critical for breast cancer growth. This occurs via the association of the pleckstrin homology (PH) domain with Akt/PKB as a key signalling event of PARs. Other PH-domain signal-proteins such as Etk/Bmx and Vav3 also associate with PAR1 and PAR2 through their PH domains. PAR1 and PAR2 bind with priority to Etk/Bmx. A point mutation in PAR2, H349A, but not in R352A, abrogates PH-protein association and is sufficient to markedly reduce PAR2-instigated breast tumour growth in vivo and placental extravillous trophoblast (EVT) invasion in vitro. Similarly, the PAR1 mutant hPar1-7A, which is unable to bind the PH domain, reduces mammary tumours and EVT invasion, endowing these motifs with physiological significance and underscoring the importance of these previously unknown PAR1 and PAR2 PH-domain-binding motifs in both pathological and physiological invasion processes. PMID:26600192

  11. Results of peripheral laser photocoagulation in pars planitis.

    PubMed Central

    Pulido, J S; Mieler, W F; Walton, D; Kuhn, E; Postel, E; Hartz, A; Jampol, L M; Weinberg, D V; Logani, S

    1998-01-01

    PURPOSE: To determine the effect of peripheral retinal laser photocoagulation (PLP) on visual acuity, intraocular inflammation, and other ocular findings, including retinal neovascularization in eyes with pars planitis. METHODS: A retrospective chart review of eyes with pars planitis that had undergone PLP. RESULTS: Twenty-two eyes in 17 patients with pars planitis had undergone treatment with PLP at 2 centers. The mean age at the time of treatment was 19.3 years. Following treatment, mean follow-up was 16.3 months (range, 6 to 37 months). Mean visual acuity was 20/60 preoperatively and 20/50 postoperatively. This level of improvement was not statistically significant (P > .10), but there was a statistically significant decrease in the use of corticosteroids between the preoperative examination and the last postoperative examination (86% versus 27%, P < .05). There was also a statistically significant decrease in vitritis at the last follow-up (P = .0008) and a decrease in neovascularization of the vitreous base (P = .03) and in clinically apparent cystoid macular edema (P = .02). Epiretinal membranes were noted in 23% of eyes preoperatively and in 45% of eyes postoperatively. Only one of these epiretinal membranes was considered to be visually significant. One eye developed a tonic dilated pupil, which slowly improved. CONCLUSIONS: Although the long-term natural history of clinical findings in pars planitis is not well documented, PLP appears to decrease the need for corticosteroids while stabilizing visual acuity. It also appears to decrease vitreous inflammation. PLP has few complications and should be considered in patients with pars planitis who are unresponsive or have adverse reactions to corticosteroids. PMID:10360286

  12. The copper-catalysed Suzuki-Miyaura coupling of alkylboron reagents: disproportionation of anionic (alkyl)(alkoxy)borates to anionic dialkylborates prior to transmetalation.

    PubMed

    Basnet, Prakash; Thapa, Surendra; Dickie, Diane A; Giri, Ramesh

    2016-09-25

    We report the first example of Cu(I)-catalysed coupling of alkylboron reagents with aryl and heteroaryl iodides that affords products in good to excellent yields. Preliminary mechanistic studies with alkylborates indicate that the anionic (alkoxy)(alkyl)borates, generated from alkyllithium and alkoxyboron reagents, undergo disproportionation to anionic dialkylborates and that both anionic alkylborates are active for transmetalation to a Cu(I)-catalyst. Results from a radical clock experiment and the Hammett plot imply that the reaction likely proceeds via a non-radical pathway. PMID:27540605

  13. Unprecedented influence of remote substituents on reactivity and stereoselectivity in Cu(I)-catalysed [2 + 2] photocycloaddition. An approach towards the synthesis of tricycloclavulone.

    PubMed

    Mondal, Sujit; Yadav, Ram Naresh; Ghosh, Subrata

    2011-07-01

    Cu(I)-catalysed [2 + 2] photocycloaddition of 1,6-dienes embedded in a furano sugar is described in connection to a synthetic approach to an abnormal marine prostanoid tricycloclavulone. An unprecedented influence of remote substituents on the reactivity and stereoselectivity of the photocycloaddition reaction has been uncovered during this investigation. While an alkene substituent inhibits cycloaddition through steric effects, a substituent having a hydroxyl or alkoxy group at the same location facilitates cycloaddition exclusively from its own side. This investigation has led to the synthesis of a functionalised 5,4-fused core unit of tricycloclavulone. PMID:21573291

  14. Enzyme-substrate complementarity governs access to a cationic reaction manifold in the P450(BM3)-catalysed oxidation of cyclopropyl fatty acids.

    PubMed

    Cryle, Max J; Hayes, Patricia Y; De Voss, James J

    2012-12-01

    The products of cytochrome P450(BM3)-catalysed oxidation of cyclopropyl-containing dodecanoic acids are consistent with the presence of a cationic reaction intermediate, which results in efficient dehydrogenation of the rearranged probes by the enzyme. These results highlight the importance of enzyme-substrate complementarity, with a cationic intermediate occurring only when the probes used begin to diverge from ideal substrates for this enzyme. This also aids in reconciling literature reports supporting the presence of cationic intermediates with certain cytochrome P450 enzyme/substrate pairs. PMID:23109039

  15. A new approach to determine the stereospecificity in lipase catalysed hydrolysis using circular dichroism (CD): lipases produce optically active diglycerides from achiral triglycerides.

    PubMed

    Uzawa, H; Nishida, Y; Ohrui, H; Meguro, H

    1990-04-30

    We describe a sensitive CD method for determining the stereospecificity in lipase (E.C.3.1.1.3) catalysed hydrolysis of triacyl glycerols into diacyl glycerols. The diglycerols were converted to chiral tert-butyldimethylsilylated 1,2- or 2,3-di-O-benzoyl-sn-glycerol (5 or 5'), and their CD was measured. This approach showed for the first time that lipases produce optically active diacyl glycerides from achiral tripalmitin and tribenzoyl glyceride with a variable extent of enantioselectivity depending on the acyl groups and the enzymes.

  16. Catalysis in the Service of Green Chemistry: Nobel Prize-Winning Palladium-Catalysed Cross-Couplings, Run in Water at Room Temperature

    PubMed Central

    Lipshutz, Bruce H.; Taft, Benjamin R.; Abela, Alexander R.; Ghorai, Subir; Krasovskiy, Arkady; Duplais, Christophe

    2012-01-01

    Palladium-catalysed cross-couplings, in particular Heck, Suzuki-Miyaura and Negishi reactions developed over three decades ago, are routinely carried out in organic solvents. However, alternative media are currently of considerable interest given an increasing emphasis on making organic processes ‘greener’; for example, by minimising organic waste in the form of organic solvents. Water is the obvious leading candidate in this regard. Hence, this review focuses on the application of micellar catalysis, in which a ‘designer’ surfactant enables these award-winning coupling reactions to be run in water at room temperature. PMID:23555153

  17. NMR studies on mechanism of isomerisation of fructose 6-phosphate to glucose 6-phosphate catalysed by phosphoglucose isomerase from Thermococcus kodakarensis.

    PubMed

    Abbas, Shahzada Nadeem; Mok, Kenneth Hun; Rashid, Naeem; Xie, Yongjing; Ruether, Manuel; O'Brien, John; Akhtar, Muhammad

    2016-06-01

    The fate of hydrogen atoms at C-2 of glucose 6-phosphate (G6P) and C-1 of fructose 6-phosphate (F6P) was studied in the reaction catalysed by phosphoglucose isomerase from Thermococcus kodakarensis (TkPGI) through 1D and 2D NMR methods. When the reaction was performed in (2)H2O the hydrogen atoms in the aforementioned positions were exchanged with deuterons indicating that the isomerization occurred by a cis-enediol intermediate involving C-1 pro-R hydrogen of F6P. These features are similar to those described for phosphoglucose isomerases from rabbit muscle and Pyrococcus furiosus.

  18. Intestinal elimination of sparfloxacin, fleroxacin, and ciprofloxacin in rats.

    PubMed Central

    Rubinstein, E; Dautrey, S; Farinoti, R; St Julien, L; Ramon, J; Carbon, C

    1995-01-01

    The intestinal transepithelial elimination of sparfloxacin and fleroxacin was compared with that of ciprofloxacin in a rat model following a single parenteral administration of 25 mg of each of the antibiotics per kg of body weight. All three fluoroquinolones were eliminated through the small intestine. Ciprofloxacin was eliminated in the proximal jejunum at a rate of 1.97 +/- 0.70 micrograms/cm2, while the elimination rates of fleroxacin and sparfloxacin were 0.64 +/- 026 and 0.21 +/- 0.10 micrograms/cm2, respectively, over a 90-min collection period. In the ileum, the elimination rates of ciprofloxacin, fleroxacin, and sparfloxacin over the same period were 1.44 +/- 0.77, 1.00 +/- 0.33, and 0.41 +/- 0.26 micrograms/mc2, respectively. These data suggest that these fluoroquinolones undergo a transepithelial elimination process in the small intestine. This route of elimination may be important in the therapy of bacterial diarrhea. PMID:7695338

  19. Environmental assessment for the natural fluctuation of water level in Par Pond and reduced water flow in Steel Creek below L-Lake at the Savannah River Site

    SciTech Connect

    1995-08-01

    The Savannah River Operations Office Strategic Plan directs Savannah River Site (SRS) to find ways to reduce operating costs, and to determine what site infrastructure must be maintained and what infrastructure is surplus. Because of the mission change, L-Lake, Par Pond, and the river water system are no longer needed to support current missions and therefore provide an opportunity for operating cost reduction. If SRS determines that L-Lake, Par Pond, and the river water system are no longer needed to support future missions and are considered surplus, appropriate NEPA documentation will be prepared. The purpose of the proposed action in this Environmental Assessment is to begin an examination of the need for the Site`s river water system by (1) developing data needed to evaluate the potential environmental impacts of further reducing or eliminating the flow demands from the Site`s river water system and; (2) evaluating the potential of reducing operating costs by allowing the water level in Par Pond to fluctuate naturally through reduced pumping. This action also includes reducing the current flow rates from L-Lake to Steel Creek to natural stream flows while maintaining full pool. The recently approved Par Pond CERCLA Interim Action Proposed Plan (IAPP) committed to evaluate in a NEPA document the environmental consequences of this proposed action. This document evaluated the remediation of human health and ecological risks associated with the three year drawdown of Par Pond. Should any of the parameters sampled in the reservoir and streams (e.g., water quality, biota, etc.) exceed established threshold levels during the implementation of the proposed action, water would again be pumped into the reservoir to minimize any impacts by bringing the water level back to an appropriate level about 58.2 m (195 ft).

  20. The role of pars flaccida in human middle ear sound transmission.

    PubMed

    Aritomo, H; Goode, R L; Gonzalez, J

    1988-04-01

    The role of the pars flaccida in middle ear sound transmission was studied with the use of twelve otoscopically normal, fresh, human temporal bones. Peak-to-peak umbo displacement in response to a constant sound pressure level at the tympanic membrane was measured with a noncontacting video measuring system capable of repeatable measurements down to 0.2 micron. Measurements were made before and after pars flaccida modifications at 18 frequencies between 100 and 4000 Hz. Four pars flaccida modifications were studied: (1) acoustic insulation of the pars flaccida to the ear canal with a silicone rubber baffle, (2) stiffening the pars flaccida with cyanoacrylate cement, (3) decreasing the tension of the pars flaccida with a nonperforating incision, and (4) perforation of the pars flaccida. All of the modifications (except the perforation) had a minimal effect on umbo displacement; this seems to imply that the pars flaccida has a minor acoustic role in human beings. PMID:3132684

  1. Endotoxin Elimination in Patients with Septic Shock: An Observation Study.

    PubMed

    Adamik, Barbara; Zielinski, Stanislaw; Smiechowicz, Jakub; Kübler, Andrzej

    2015-12-01

    To evaluate the effectiveness of endotoxin elimination with an adsorption column in patients with septic shock and endotoxemia. The elimination therapy was guided by a new bedside method of measuring endotoxin activity (EA). Intensive care unit (ICU) patients with septic shock and suspected Gram-negative infection were consecutively added to the study group within the first 24 h. Endotoxin elimination was performed using hemoperfusion with the Alteco LPS Adsorber. The primary endpoint was improvement in organ function within the first 24 h of treatment. A secondary objective was to assess the usefulness of a new method of measuring EA to help guide endotoxin elimination therapy. Out of 64 patients 18 had a high baseline EA [0.70 EA units (0.66-0.77)]. Those patients had endotoxin elimination treatment in addition to conventional medical therapy. At 24 h after endotoxin elimination, the EA had decreased to 0.56 EA units (0.43-0.77), (p = 0.005); MAP increased from 69 (62-80) to 80 mm Hg (68-88), (p = 0.002), and noradrenaline use decreased from 0.28 (0.15-0.80) to 0.1 μg/kg/min (0.00-0.70) at the same time (p = 0.04). The SOFA score had decreased from 11 (9-15) to 9 (7-14) points 24 h after endotoxin elimination (p = 0.01) with a median delta SOFA -2 points. Endotoxin elimination did not have a significant effect on the ICU length of stay or ICU mortality. Effective endotoxin elimination resulted in a significant improvement in hemodynamic parameters and of organ function. The application of the EA assay was useful for the bedside monitoring of endotoxemia in critically ill ICU patients.

  2. Time to set the agenda for schistosomiasis elimination.

    PubMed

    Rollinson, David; Knopp, Stefanie; Levitz, Sarah; Stothard, J Russell; Tchuem Tchuenté, Louis-Albert; Garba, Amadou; Mohammed, Khalfan A; Schur, Nadine; Person, Bobbie; Colley, Daniel G; Utzinger, Jürg

    2013-11-01

    It is time to raise global awareness to the possibility of schistosomiasis elimination and to support endemic countries in their quest to determine the most appropriate approaches to eliminate this persistent and debilitating disease. The main interventions for schistosomiasis control are reviewed, including preventive chemotherapy using praziquantel, snail control, sanitation, safe water supplies, and behaviour change strategies supported by information, education and communication (IEC) materials. Differences in the biology and transmission of the three main Schistosoma species (i.e. Schistosoma haematobium, S. mansoni and S. japonicum), which impact on control interventions, are considered. Sensitive diagnostic procedures to ensure adequate surveillance in areas attaining low endemicity are required. The importance of capacity building is highlighted. To achieve elimination, an intersectoral approach is necessary, with advocacy and action from local communities and the health community to foster cooperative ventures with engineers, the private sector, governments and non-governmental organizations specialized in water supply and sanitation. Examples of successful schistosomiasis control programmes are reviewed to highlight what has been learnt in terms of strategy for control and elimination. These include St. Lucia and other Caribbean islands, Brazil and Venezuela for S. mansoni; Saudi Arabia and Egypt for both S. mansoni and S. haematobium; Morocco, Tunisia, Algeria, Mauritius and the Islamic Republic of Iran for S. haematobium; Japan and the People's Republic of China for S. japonicum. Additional targets for elimination or even eradication could be the two minor human schistosome species S. guineenisis and S. intercalatum, which have a restricted distribution in West and Central Africa. The examples show that elimination of schistosomiasis is an achievable and desirable goal requiring full integration of preventive chemotherapy with the tools of transmission

  3. Aspergillus nidulans alpha-galactosidase of glycoside hydrolase family 36 catalyses the formation of alpha-galacto-oligosaccharides by transglycosylation.

    PubMed

    Nakai, Hiroyuki; Baumann, Martin J; Petersen, Bent O; Westphal, Yvonne; Hachem, Maher Abou; Dilokpimol, Adiphol; Duus, Jens Ø; Schols, Henk A; Svensson, Birte

    2010-09-01

    The alpha-galactosidase from Aspergillus nidulans (AglC) belongs to a phylogenetic cluster containing eukaryotic alpha-galactosidases and alpha-galacto-oligosaccharide synthases of glycoside hydrolase family 36 (GH36). The recombinant AglC, produced in high yield (0.65 g.L(-1) culture) as His-tag fusion in Escherichia coli, catalysed efficient transglycosylation with alpha-(1-->6) regioselectivity from 40 mm 4-nitrophenol alpha-d-galactopyranoside, melibiose or raffinose, resulting in a 37-74% yield of 4-nitrophenol alpha-D-Galp-(1-->6)-D-Galp, alpha-D-Galp-(1-->6)-alpha-D-Galp-(1-->6)-D-Glcp and alpha-D-Galp-(1-->6)-alpha-D-Galp-(1-->6)-D-Glcp-(alpha1-->beta2)-d-Fruf (stachyose), respectively. Furthermore, among 10 monosaccharide acceptor candidates (400 mm) and the donor 4-nitrophenol alpha-D-galactopyranoside (40 mm), alpha-(1-->6) linked galactodisaccharides were also obtained with galactose, glucose and mannose in high yields of 39-58%. AglC did not transglycosylate monosaccharides without the 6-hydroxymethyl group, i.e. xylose, L-arabinose, L-fucose and L-rhamnose, or with axial 3-OH, i.e. gulose, allose, altrose and L-rhamnose. Structural modelling using Thermotoga maritima GH36 alpha-galactosidase as the template and superimposition of melibiose from the complex with human GH27 alpha-galactosidase supported that recognition at subsite +1 in AglC presumably requires a hydrogen bond between 3-OH and Trp358 and a hydrophobic environment around the C-6 hydroxymethyl group. In addition, successful transglycosylation of eight of 10 disaccharides (400 mm), except xylobiose and arabinobiose, indicated broad specificity for interaction with the +2 subsite. AglC thus transferred alpha-galactosyl to 6-OH of the terminal residue in the alpha-linked melibiose, maltose, trehalose, sucrose and turanose in 6-46% yield and the beta-linked lactose, lactulose and cellobiose in 28-38% yield. The product structures were identified using NMR and ESI-MS and five of the 13

  4. Cutaneous tuberculosis with a difference: Documenting transfollicular elimination of granulomas.

    PubMed

    Desai, Chirag A; Khopkar, Uday

    2016-01-01

    A patient presented with a an asymptomatic brown to erythematous, scaly indurated solitary plaque on his elbow. The lesion was diagnosed as lupus vulgaris on the basis of clinical features and biopsy findings. The histopathology further revealed a granuloma within the follicular infundibulum, which was possibly being expelled out. The phenomenon of transepidermal elimination has been described previously in many conditions, including cutaneous tuberculosis; however, transfollicular elimination of the granuloma has not been reported. We report this unusual phenomenon as a possible mode of elimination of the granuloma. PMID:27559508

  5. Commitment of measles elimination by 2020: challenges in India.

    PubMed

    Vaidya, S R

    2015-02-01

    The eleven member states of World Health Organization South-East Asia Region committed to eliminate measles by 2020. In phased manner, Government of India is working on this goal, and has introduced two-dose strategy for measles vaccine in the routine immunization. Molecular epidemiology of measles in India has been considerably growing that would be useful for understanding the circulation of wild type measles in pre- and post-elimination period. However, importations of cases from other countries may be likely. This article describes major challenges to achieve the measles elimination goal in India.

  6. Cutaneous tuberculosis with a difference: Documenting transfollicular elimination of granulomas

    PubMed Central

    Desai, Chirag A.; Khopkar, Uday

    2016-01-01

    A patient presented with a an asymptomatic brown to erythematous, scaly indurated solitary plaque on his elbow. The lesion was diagnosed as lupus vulgaris on the basis of clinical features and biopsy findings. The histopathology further revealed a granuloma within the follicular infundibulum, which was possibly being expelled out. The phenomenon of transepidermal elimination has been described previously in many conditions, including cutaneous tuberculosis; however, transfollicular elimination of the granuloma has not been reported. We report this unusual phenomenon as a possible mode of elimination of the granuloma. PMID:27559508

  7. Do Protozoa Control the Elimination of Vibrio choleraein Brackish Water?

    NASA Astrophysics Data System (ADS)

    Martínez Pérez, María Elena; Macek, Miroslav; Castro Galván, María Teresa

    2004-05-01

    Elimination of inoculated Vibrio cholerae (107 cells ml-1) within a brackish water bacteria assemblage (Mecoacán Lagoon, State of Tabasco, Mexico) was studied in laboratory microcosms with filtration-fractionated water. Feeding of a ciliate, Cyclidium glaucoma was evaluated using fluorescently labelled V. cholerae o1. Even though V. cholerae was not exploited as the major food source, ciliates were able to eliminate it efficiently. An addition of chitin directly supported the growth of bacteria, although not so much of V. cholerae, and indirectly the growth of the protistan assemblage. Generally, the changes in a bacterial assemblage structure were the most important in V. cholerae elimination.

  8. Quinoprotein-catalysed reactions.

    PubMed Central

    Anthony, C

    1996-01-01

    This review is concerned with the structure and function of the quinoprotein enzymes, sometimes called quinoenzymes. These have prosthetic groups containing quinones, the name thus being analogous to the flavoproteins containing flavin prosthetic groups. Pyrrolo-quinoline quinone (PQQ) is non-covalently attached, whereas tryptophan tryptophylquinone (TTQ), topaquinone (TPQ) and lysine tyrosylquinone (LTQ) are derived from amino acid residues in the backbone of the enzymes. The mechanisms of the quinoproteins are reviewed and related to their recently determined three-dimensional structures. As expected, the quinone structures in the prosthetic groups play important roles in the mechanisms. A second common feature is the presence of a catalytic base (aspartate) at the active site which initiates the reactions by abstracting a proton from the substrate, and it is likely to be involved in multiple reactions in the mechanism. A third common feature of these enzymes is that the first part of the reaction produces a reduced prosthetic group; this part of the mechanism is fairly well understood. This is followed by an oxidative phase involving electron transfer reactions which remain poorly understood. In both types of dehydrogenase (containing PQQ and TTQ), electrons must pass from the reduced prosthetic group to redox centres in a second recipient protein (or protein domain), whereas in amine oxidases (containing TPQ or LTQ), electrons must be transferred to molecular oxygen by way of a redox-active copper ion in the protein. PMID:9003352

  9. Is There an "F" in Your PAR? Understanding, Teaching and Doing Action Research

    ERIC Educational Resources Information Center

    Lorenzetti, Liza; Walsh, Christine Ann

    2014-01-01

    Participatory Action Research (PAR) is increasingly recognized within academic research and pedagogy. What are the benefits of including feminism within participatory action research and teaching? In responding to this question, we discuss the similarities and salient differences between PAR and feminist informed PAR (FPAR). There are eight themes…

  10. ParA resolvase catalyzes site-specific excision of DNA from the Arabidopsis genome

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The small serine resolvase ParA from bacterial plasmids RK2 and RP4 catalyzes the recombination of two identical 133 bp recombination sites known as MRS. Previously, we reported that ParA is active in the fission yeast Schizosaccharomyces pombe. In this work, the parA recombinase gene was placed un...

  11. The Role of Prostate Apoptosis Response-4 (Par-4) in Mycobacterium tuberculosis Infected Macrophages

    PubMed Central

    Han, Ji-Ye; Lim, Yun-Ji; Choi, Ji-Ae; Lee, Jung-hwan; Jo, Sung-Hee; Oh, Sung-Man; Song, Chang-Hwa

    2016-01-01

    Prostate apoptosis response-4 (Par-4) is a tumor suppressor protein that forms a complex with glucose-regulated protein 78 (GRP78) to induce apoptosis. Previously, we reported that ER stress-induced apoptosis is a critical host defense mechanism against Mycobacterium tuberculosis (Mtb). We sought to understand the role of Par-4 during ER stress-induced apoptosis in response to mycobacterial infection. Par-4 and GRP78 protein levels increased in response Mtb (strain: H37Ra) infection. Furthermore, Par-4 and GRP78 translocate to the surface of Mtb H37Ra-infected macrophages and induce apoptosis via caspase activation. NF-κB activation, Mtb-mediated ER stress, and Par-4 production were significantly diminished in macrophages with inhibited ROS production. To test Par-4 function during mycobacterial infection, we analyzed intracellular survival of Mtb H37Ra in macrophages with Par-4 overexpression or knockdown. Mtb H37Ra growth was significantly reduced in Par-4 overexpressing macrophages and increased in knockdown macrophages. We also observed increased Par-4, GRP78, and caspases activation in Bacillus Calmette-Guérin (BCG)-infected prostate cancer cells. Our data demonstrate that Par-4 is associated with ER stress-induced apoptosis resulting in reduced intracellular survival of mycobacteria. BCG treatment increases Par-4-dependent caspase activation in prostate cancer cells. These results suggest ER stress-induced Par-4 acts as an important defense mechanism against mycobacterial infection and regulates cancer. PMID:27552917

  12. Alternative 3' UTR selection controls PAR-5 homeostasis and cell polarity in C. elegans embryos.

    PubMed

    Mikl, Martin; Cowan, Carrie R

    2014-09-11

    Cell polarity in one-cell C. elegans embryos guides asymmetric cell division and cell-fate specification. Shortly after fertilization, embryos establish two antagonistic cortical domains of PAR proteins. Here, we find that the conserved polarity factor PAR-5 regulates PAR domain size in a dose-dependent manner. Using quantitative imaging and controlled genetic manipulation, we find that PAR-5 protein levels reflect the cumulative output of three mRNA isoforms with different translational efficiencies mediated by their 3' UTRs. 3' UTR selection is regulated, influencing PAR-5 protein abundance. Alternative splicing underlies the selection of par-5 3' UTR isoforms. 3' UTR splicing is enhanced by the SR protein kinase SPK-1, and accordingly, SPK-1 is required for wild-type PAR-5 levels and PAR domain size. Precise regulation of par-5 isoform selection is essential for polarization when the posterior PAR network is compromised. Together, strict control of PAR-5 protein levels and feedback from polarity to par-5 3' UTR selection confer robustness to embryo polarization. PMID:25199833

  13. Biased signalling and proteinase-activated receptors (PARs): targeting inflammatory disease.

    PubMed

    Hollenberg, M D; Mihara, K; Polley, D; Suen, J Y; Han, A; Fairlie, D P; Ramachandran, R

    2014-03-01

    Although it has been known since the 1960s that trypsin and chymotrypsin can mimic hormone action in tissues, it took until the 1990s to discover that serine proteinases can regulate cells by cleaving and activating a unique four-member family of GPCRs known as proteinase-activated receptors (PARs). PAR activation involves the proteolytic exposure of its N-terminal receptor sequence that folds back to function as a 'tethered' receptor-activating ligand (TL). A key N-terminal arginine in each of PARs 1 to 4 has been singled out as a target for cleavage by thrombin (PARs 1, 3 and 4), trypsin (PARs 2 and 4) or other proteases to unmask the TL that activates signalling via Gq , Gi or G12 /13 . Similarly, synthetic receptor-activating peptides, corresponding to the exposed 'TL sequences' (e.g. SFLLRN-, for PAR1 or SLIGRL- for PAR2) can, like proteinase activation, also drive signalling via Gq , Gi and G12 /13 , without requiring receptor cleavage. Recent data show, however, that distinct proteinase-revealed 'non-canonical' PAR tethered-ligand sequences and PAR-activating agonist and antagonist peptide analogues can induce 'biased' PAR signalling, for example, via G12 /13 -MAPKinase instead of Gq -calcium. This overview summarizes implications of this 'biased' signalling by PAR agonists and antagonists for the recognized roles the PARs play in inflammatory settings. PMID:24354792

  14. Independent Confirmation of the MODIS LAI/fPAR Algorithm

    NASA Astrophysics Data System (ADS)

    Ganapol, B. D.; Dungan, J. L.

    2001-12-01

    The Leaf Canopy Model (LCM)-2 is a nested model that combines leaf radiative transfer with a full canopy reflectance model through the phase function (Ganapol et al. 1999). The basic components of the model include inversion for a leaf scattering coefficient, construction of a representative absorption coefficient and the determination of canopy reflectance given leaf area index (LAI) values and information on canopy type and structure. It can also be used to calculate the fraction of absorbed photosynthetically active radiation (fPAR) for the canopy. It therefore serves as an independent means of confirming the results of the MOD15 algorithm (Knyazikhin et al. 1998) that produces LAI and fPAR fields from reflectance measured by the Moderate Resolution Imaging Spectrometer (MODIS). In LCM2, relatively simple first principles of radiative transfer are used whereas in the MOD15 algorithm, scene variability is accounted for by specifying distributions and a response surface in a table-lookup procedure. The distributions are generated by various radiative transfer models with a host of underlying assumptions. The attempt to compare results from these two models is a useful means of addressing the structural uncertainty in the Earth Observing System prediction problem. We compared LCM2 results with those from the MOD15 algorithm for fPAR calculation. 100 pixels for an EOS Core Validation Site where there were coincident reflectance, vegetation index, fPAR and LAI products were chosen. The 8-day 500 m reflectance product was spatially degraded to coincide with 8-day 1 km LAI and fPAR products and LAI and land cover products were used to parameterize LCM2. Most fPAR results agreed to within 10 percent, though a bias was observed. Poor agreement was seen with vegetation index products. Ganapol, B.D., L.F. Johnson, C.A. Hlavka, D.L. Peterson, and B. Bond, LCM2: A coupled leaf/canopy radiative transfer model, Remote Sensing of Environment, 70:153-166, 1999. Knyazikhin, Y., J

  15. ParCAT: A Parallel Climate Analysis Toolkit

    NASA Astrophysics Data System (ADS)

    Haugen, B.; Smith, B.; Steed, C.; Ricciuto, D. M.; Thornton, P. E.; Shipman, G.

    2012-12-01

    Climate science has employed increasingly complex models and simulations to analyze the past and predict the future of our climate. The size and dimensionality of climate simulation data has been growing with the complexity of the models. This growth in data is creating a widening gap between the data being produced and the tools necessary to analyze large, high dimensional data sets. With single run data sets increasing into 10's, 100's and even 1000's of gigabytes, parallel computing tools are becoming a necessity in order to analyze and compare climate simulation data. The Parallel Climate Analysis Toolkit (ParCAT) provides basic tools that efficiently use parallel computing techniques to narrow the gap between data set size and analysis tools. ParCAT was created as a collaborative effort between climate scientists and computer scientists in order to provide efficient parallel implementations of the computing tools that are of use to climate scientists. Some of the basic functionalities included in the toolkit are the ability to compute spatio-temporal means and variances, differences between two runs and histograms of the values in a data set. ParCAT is designed to facilitate the "heavy lifting" that is required for large, multidimensional data sets. The toolkit does not focus on performing the final visualizations and presentation of results but rather, reducing large data sets to smaller, more manageable summaries. The output from ParCAT is provided in commonly used file formats (NetCDF, CSV, ASCII) to allow for simple integration with other tools. The toolkit is currently implemented as a command line utility, but will likely also provide a C library for developers interested in tighter software integration. Elements of the toolkit are already being incorporated into projects such as UV-CDAT and CMDX. There is also an effort underway to implement portions of the CCSM Land Model Diagnostics package using ParCAT in conjunction with Python and gnuplot. Par

  16. Diffusion filter eliminates fringe effects of coherent laser light source

    NASA Technical Reports Server (NTRS)

    Olsasky, M. J.

    1970-01-01

    Diffusion filter comprised of small particles in colloidal suspension reduces the coherence of a laser beam used as a photographic light source. Interference patterns which obscure details in photographic film are eliminated, the intensity and collimation are moderately affected.

  17. Elimination of protease-inhibitor complexes from the arthritic joint.

    PubMed

    Ekerot, L; Ohlsson, K; Necking, L

    1985-01-01

    In the rheumatic joint, destructive proteolytic enzymes are released and counteracted by complexation to the predominant inhibitors alpha 2-macroglobulin and alpha 1-antitrypsin. The articular elimination of these complexes is thought to be of decisive importance in the protease-inhibitor interplay influencing the inhibitory capacity of the synovial fluid. Protease-alpha 2-macroglobulin complexes showed an intraarticular half-life shorter than 2 hours in arthritis and were eliminated by various routes including phagocytosis in cells of the synovial membrane and in regional lymph nodes, in addition to haematogenous resorption and uptake in the liver. The phagocytosed complexes were degraded to low-molecular-weight metabolites excretable in the urine. The articular elimination of elastase-alpha 1-antitrypsin complexes seemed to be an equivalent process, but an additional intrasynovial dissociation of the complexes was also indicated. Thus the intraarticularly released elastase seemed to be bound and eliminated in complex with alpha 2-macroglobulin. PMID:2414244

  18. [Molecular surveillance shows progress in measles elimination process].

    PubMed

    Santibanez, S; Mankertz, A

    2013-09-01

    Measles is a severe disease caused by infection with the measles virus. Complications after the onset of infection lead to 1-3 fatalities per 1,000 cases in industrialized countries. If more than 95 % of the global population were vaccinated twice with the measles, mumps, and rubella (MMR) vaccine, measles could be eliminated worldwide. The elimination of measles and rubella should be reached in the WHO Europe region in 2015. One important criterion for elimination of the measles virus consists in the analysis of the duration of transmission chains initiated by the import of measles virus. To assign measles viruses to outbreaks and transmission chains, genetic characterization is necessary. These investigations have been performed continually at the National Reference Center Measles, Mumps, Rubella since 1999, when the German Intervention Program was launched. This article summarizes our experiences with measles virus genotyping and new developments with respect to measles elimination in Germany. PMID:23990085

  19. Saturation current spikes eliminated in saturable core transformers

    NASA Technical Reports Server (NTRS)

    Schwarz, F. C.

    1971-01-01

    Unsaturating composite magnetic core transformer, consisting of two separate parallel cores designed so impending core saturation causes signal generation, terminates high current spike in converter primary circuit. Simplified waveform, demonstrates transformer effectiveness in eliminating current spikes.

  20. β-Alkyl Elimination: Fundamental Principles and Some Applications.

    PubMed

    O'Reilly, Matthew E; Dutta, Saikat; Veige, Adam S

    2016-07-27

    This review describes organometallic compounds and materials that are capable of mediating a rarely encountered but fundamentally important reaction: β-alkyl elimination at the metal-Cα-Cβ-R moiety, in which an alkyl group attached to the Cβ atom is transferred to the metal or to a coordinated substrate. The objectives of this review are to provide a cohesive fundamental understanding of β-alkyl-elimination reactions and to highlight its applications in olefin polymerization, alkane hydrogenolysis, depolymerization of branched polymers, ring-opening polymerization of cycloalkanes, and other useful organic reactions. To provide a coherent understanding of the β-alkyl elimination reaction, special attention is given to conditions and strategies used to facilitate β-alkyl-elimination/transfer events in metal-catalyzed olefin polymerization, which provide the well-studied examples.

  1. [Molecular surveillance shows progress in measles elimination process].

    PubMed

    Santibanez, S; Mankertz, A

    2013-09-01

    Measles is a severe disease caused by infection with the measles virus. Complications after the onset of infection lead to 1-3 fatalities per 1,000 cases in industrialized countries. If more than 95 % of the global population were vaccinated twice with the measles, mumps, and rubella (MMR) vaccine, measles could be eliminated worldwide. The elimination of measles and rubella should be reached in the WHO Europe region in 2015. One important criterion for elimination of the measles virus consists in the analysis of the duration of transmission chains initiated by the import of measles virus. To assign measles viruses to outbreaks and transmission chains, genetic characterization is necessary. These investigations have been performed continually at the National Reference Center Measles, Mumps, Rubella since 1999, when the German Intervention Program was launched. This article summarizes our experiences with measles virus genotyping and new developments with respect to measles elimination in Germany.

  2. Adhesive-backed terminal board eliminates mounting screws

    NASA Technical Reports Server (NTRS)

    1965-01-01

    Low-profile terminal board is used in dense electronic circuits where mounting and working space is limited. The board has a thin layer of pressure-sensitive adhesive backing which eliminates the need for mounting screws.

  3. SORPTION ON WASTEWATER SOLIDS: ELIMINATION OF BIOLOGICAL ACTIVITY

    EPA Science Inventory

    Sorption was found to be greatly affected by the biological activity in wastewater solids. wo experimental techniques, cyanide treatment and pasteurization, were developed for eliminating the biological activity during isotherm measurements. oth methods are effective; however, pa...

  4. Glucose and fructose to platform chemicals: understanding the thermodynamic landscapes of acid-catalysed reactions using high-level ab initio methods.

    PubMed

    Assary, Rajeev S; Kim, Taejin; Low, John J; Greeley, Jeff; Curtiss, Larry A

    2012-12-28

    Molecular level understanding of acid-catalysed conversion of sugar molecules to platform chemicals such as hydroxy-methyl furfural (HMF), furfuryl alcohol (FAL), and levulinic acid (LA) is essential for efficient biomass conversion. In this paper, the high-level G4MP2 method along with the SMD solvation model is employed to understand detailed reaction energetics of the acid-catalysed decomposition of glucose and fructose to HMF. Based on protonation free energies of various hydroxyl groups of the sugar molecule, the relative reactivity of gluco-pyranose, fructo-pyranose and fructo-furanose are predicted. Calculations suggest that, in addition to the protonated intermediates, a solvent assisted dehydration of one of the fructo-furanosyl intermediates is a competing mechanism, indicating the possibility of multiple reaction pathways for fructose to HMF conversion in aqueous acidic medium. Two reaction pathways were explored to understand the thermodynamics of glucose to HMF; the first one is initiated by the protonation of a C2-OH group and the second one through an enolate intermediate involving acyclic intermediates. Additionally, a pathway is proposed for the formation of furfuryl alcohol from glucose initiated by the protonation of a C2-OH position, which includes a C-C bond cleavage, and the formation of formic acid. The detailed free energy landscapes predicted in this study can be used as benchmarks for further exploring the sugar decomposition reactions, prediction of possible intermediates, and finally designing improved catalysts for biomass conversion chemistry in the future. PMID:22932938

  5. Slow Reductive Elimination from Arylpalladium Parent Amido Complexes

    PubMed Central

    Klinkenberg, Jessica L.; Hartwig, John F.

    2010-01-01

    We report reductive eliminations of primary arylamines from a series of bisphosphine-ligated arylpalladium(II) parent amido complexes that counter several established trends. In contrast to arylamido and alkylamido complexes of the aromatic bisphosphines DPPF and BINAP, parent amido complexes, do not form or undergo reductive elimination of monoarylamines. However, arylpalladium parent amido complexes ligated by the alkylbisphosphine CyPF-t-Bu form in good yield and undergo reductive elimination. Despite the basicity of parent amido ligand and the typically faster reductive elimination from complexes containing more basic amido ligands, the CyPF-t-Bu-ligated arylpalladium parent amido complexes undergo reductive elimination much more slowly than the analogous complexes containing arylamido or alkylamido ligands. Moreover, the parent amido complexes form more rapidly and are more stable thermodynamically in a series of exchange processes than the arylamido complexes. Computational studies support the overriding influence of steric effects on the stability and reactivity of the parent amido complex. The slow rate of reductive elimination causes the arylpalladium amido complex to be the resting state of the coupling of aryl halides with ammonia catalyzed by CyPF-t-Bu-ligated palladium, and this resting state contrasts the Pd(0) or arylpalladium(II) resting states of reactions of aryl halides with amines catalyzed by most palladium complexes. PMID:20695642

  6. Leprosy: too complex a disease for a simple elimination paradigm.

    PubMed Central

    Lockwood, Diana N. J.; Suneetha, Sujai

    2005-01-01

    Can leprosy be eliminated? This paper considers the question against the background of the WHO programme to eliminate leprosy. In 1991 the World Health Assembly set a target of eliminating leprosy as a public health problem by 2000. Elimination was defined as reaching a prevalence of < 1 case per 10 000 people. The elimination programme has been successful in delivering highly effective antibiotic therapy worldwide. However, despite this advance, new-case detection rates remain stable in countries with the highest rates of endemic leprosy, such as Brazil and India. This suggests that infection has not been adequately controlled by antibiotics alone. Leprosy is perhaps more appropriately classed as a chronic stable disease than as an acute infectious disease responsive to elimination strategies. In many countries activities to control and treat leprosy are being integrated into the general health-care system. This reduces the stigma associated with leprosy. However, leprosy causes long-term immunological complications, disability and deformity. The health-care activities of treating and preventing disabilities need to be provided in an integrated setting. Detecting new cases and monitoring disability caused by leprosy will be a challenge. One solution is to implement long-term surveillance in selected countries with the highest rates of endemic disease so that an accurate estimate of the burden of leprosy can be determined. It is also critical that broad-based research into this challenging disease continues until the problems are truly solved. PMID:15798849

  7. Can ivermectin mass treatments eliminate onchocerciasis in Africa?

    PubMed Central

    Winnen, M.; Plaisier, A. P.; Alley, E. S.; Nagelkerke, N. J. D.; van Oortmarssen, G.; Boatin, B. A.; Habbema, J. D. F.

    2002-01-01

    OBJECTIVE: To elucidate the conditions in which mass treatment with ivermectin reduces the transmission of Onchocerca volvulus sufficiently to eliminate infection from an African community. METHODS: ONCHOSIM, a microsimulation model for onchocerciasis transmission, was used to explore the implications of different treatment intervals, coverage levels and precontrol endemicities for the likelihood of elimination. FINDINGS: Simulations suggested that control strategies based exclusively on ivermectin mass treatments could eliminate onchocerciasis. The duration of treatment required to eliminate infection depended heavily on the treatment programme and precontrol endemicity. In areas with medium to high levels of infection, annual mass treatments with 65% coverage for at least 25 years were necessary. Model predictions suggested that durations exceeding 35 years would be required if there were much heterogeneity in exposure to vector bites and, consequently, wide individual variation in microfilaria counts. If the treatment interval were reduced from 12 to 6 months the time for completion of the programme could be more than halved and elimination could be accomplished in areas of hyperendemicity, provided that the effects of each treatment would be the same as with annual treatments. However, it was doubtful whether high coverage levels could be sustained long enough to achieve worldwide eradication. CONCLUSION: Elimination of onchocerciasis from most endemic foci in Africa appears to be possible. However, the requirements in terms of duration, coverage, and frequency of treatment may be prohibitive in highly endemic areas. PMID:12077614

  8. Elimination of amino acids in acute renal failure.

    PubMed

    Druml, W; Bürger, U; Kleinberger, G; Lenz, K; Laggner, A

    1986-01-01

    Plasma amino acid concentrations and the elimination of parenterally administered amino acids were investigated in 12 patients with nonhypercatabolic acute renal failure. A distinctive plasma amino acid pattern could be observed: plasma concentrations of phenylalanine and methionine were increased, those of valine and leucine decreased. Of the nonessential amino acids, cystine, taurine und tyrosine had elevated but none of them reduced plasma concentrations. The elimination of amino acids was evaluated in a monocompartment model after bolus injection of an amino acid solution containing essential and nonessential amino acids. Pharmacokinetic parameters of 17 amino acids were calculated. The mean elimination half-time was raised by 25%. The elimination half-time of phenylalanine, methionine, glutamic acid, proline and ornithine was increased. Histidine was the only amino acid with--however insignificantly--accelerated elimination from the intravascular compartment. The total clearance rate and total transfer rate was not altered (107 and 97% of normal, respectively). The clearance of threonine, lysine, serine, glycine and histidine was increased, of valine, phenylalanine, glutamic acid and to a minor degree of methionine was decreased. The transfer rate of methionine, lysine, glycine was elevated, of valine, aspartic acid, glutamic acid and ornithine reduced. The demonstration of these pronounced alterations of amino acid elimination in acute renal failure may have major consequences in parenteral amino acid therapy.

  9. Cross ambiguity functions on the MasPar MP-2

    SciTech Connect

    Carlson, D.A.; Pryor, D.V.; Frock, C.K.

    1995-12-01

    In a signal processing environment, cross ambiguity functions are often used to detect when one signal is a time and/or frequency shift of another. They consist of multiple cross-correlations, which can be computed efficiently using complex valued FFTs. This paper discusses the implementation of cross ambiguity functions on the MasPar MP-2, a SIMD processor array. Two different implementations are developed. The first computes each cross ambiguity function serially, using FFT code that parallelizes across the complete set of processors. The second uses the MasPar IORAM to realign the data so that the cross ambiguity functions can be computed in parallel. In this case, multiple FFTs are executed in parallel on subsets of the processors, which lowers the overall amount of communication required.

  10. Design, construction, and wire calibration of PAR BPM striplines

    NASA Astrophysics Data System (ADS)

    Sellyey, W.; Barr, D.; Erwin, L.

    1995-05-01

    The Positron Accumulator Ring (PAR) is part of the APS injection system. It received 24 30-ns FWHM bursts of 450-meV positrons, and compresses them into 6-nC, 290-ps rms bunches. Striplines were selected as beam position monitors (BPMs) to assure that good position sensitivity is achieved. This paper will describe the design, construction, and wire calibration of the 16 PAR BPMs. It will be demonstrated that all relevant stripline parameters can be determined by solving the two-dimensional LaPlace equation. This was done numerically using the electrostatic part of the PE2D computer program. The construction of the units will be briefly discussed. Wire calibration data on one of the final units will be compared with theory at four frequencies.

  11. Une alternative au cobalt pour la synthese de nanotubes de carbone monoparoi par plasma inductif thermique

    NASA Astrophysics Data System (ADS)

    Carrier, Jean-Francois

    Les nanotubes de carbone de type monoparoi (C-SWNT) sont une classe recente de nanomateriaux qui ont fait leur apparition en 1991. L'interet qu'on leur accorde provient des nombreuses proprietes d'avant-plan qu'ils possedent. Leur resistance mecanique serait des plus rigide, tout comme ils peuvent conduire l'electricite et la chaleur d'une maniere inegalee. Non moins, les C-SWNT promettent de devenir une nouvelle classe de plateforme moleculaire, en servant de site d'attache pour des groupements reactifs. Les promesses de ce type particulier de nanomateriau sont nombreuses, la question aujourd'hui est de comment les realiser. La technologie de synthese par plasma inductif thermique se situe avantageusement pour la qualite de ses produits, sa productivite et les faibles couts d'operation. Par contre, des recherches recentes ont permis de mettre en lumiere des risques d'expositions reliees a l'utilisation du cobalt, comme catalyseur de synthese; son elimination ou bien son remplacement est devenu une preoccupation importante. Quatre recettes alternatives ont ete mises a l'essai afin de trouver une alternative plus securitaire a la recette de base; un melange catalytique ternaire, compose de nickel, de cobalt et d'oxyde d'yttrium. La premiere consiste essentiellement a remplacer la proportion massique de cobalt par du nickel, qui etait deja present dans la recette de base. Les trois options suivantes contiennent de nouveaux catalyseurs, en remplacement au Co, qui sont apparus dans plusieurs recherches scientifiques au courant des dernieres annees: le dioxyde de zircone (ZrO2), dioxyde de manganese (MnO2) et le molybdene (Mo). La methode utilisee consiste a vaporiser la matiere premiere, sous forme solide, dans un reacteur plasma a haute frequence (3 MHz) a paroi refroidi. Apres le passage dans le plasma, le systeme traverse une section dite de "croissance", isolee thermiquement a l'aide de graphite, afin de maintenir une certaine plage de temperature favorable a la

  12. Macroinvertebrates of Par Pond and Pond B: Final report, January 1984-June 1985

    SciTech Connect

    Kondratieff, B.C.; Chimney, M.J.; Painter, W.B.

    1985-08-01

    This document reports on the Par Pond and Pond B macroinvertebrate sampling program from January 1984 through June 1985. It includes data on quantitative and qualitative benthic sampling, quantitative meroplankton sampling and quarterly diel sample. The basic objectives were to: (1) characterize the benthic and meroplankton macroinvertebrate communities of Par Pond and Pond B, with respect to taxonomic composition and diversity, density and relative abundance of functional feeding groups; (2) assess the impact of thermal discharges on the macroinvertebrate community of Par Pond; (3) assess the impact and significance of entrainment losses of macroinvertebrate meroplankton from Par Pond; and (4) compare Par Pond macroninvertebrate communities with those in Pond B.

  13. The Pars Interarticularis Stress Reaction, Spondylolysis, and Spondylolisthesis Progression

    PubMed Central

    Motley, Gina; Nyland, John; Jacobs, Jake; Caborn, David N. M.

    1998-01-01

    Objective: To review the classification, etiology, clinical and radiologic evaluation, and management of the pars interarticularis stress reaction, spondylolysis, and spondylolisthesis progression. Data Sources: Grateful Med was searched from 1980 to 1998 using the terms “spondylolysis,” “spondylolisthesis,” “female athlete” “spondylogenic,” and “pars interarticularis.” Data Synthesis: The progression from pars interarticularis stress reaction through spondylolysis to spondylolisthesis is common in adolescent athletes, and, because of hormonal influences and cheerleading and gymnastic maneuvers, females are particularly at risk. Proper diagnosis and management include a thorough evaluation, radiographs (possibly with technetium bone scan or single-photon emission computed tomography), activity modification, dietary counseling, a therapeutic exercise program focusing on proper trunk and hip muscle strength and extensibility balances, and education regarding proper back postures, positioning, lifting mechanics, and jump landings. Conclusions/Recommendations: The athletic trainer plays an integral part in managing this injury progression, particularly with identifying at-risk individuals and intervening appropriately. ImagesFigure 4. PMID:16558534

  14. ParB Partition Proteins: Complex Formation and Spreading at Bacterial and Plasmid Centromeres

    PubMed Central

    Funnell, Barbara E.

    2016-01-01

    In bacteria, active partition systems contribute to the faithful segregation of both chromosomes and low-copy-number plasmids. Each system depends on a site-specific DNA binding protein to recognize and assemble a partition complex at a centromere-like site, commonly called parS. Many plasmid, and all chromosomal centromere-binding proteins are dimeric helix-turn-helix DNA binding proteins, which are commonly named ParB. Although the overall sequence conservation among ParBs is not high, the proteins share similar domain and functional organization, and they assemble into similar higher-order complexes. In vivo, ParBs “spread,” that is, DNA binding extends away from the parS site into the surrounding non-specific DNA, a feature that reflects higher-order complex assembly. ParBs bridge and pair DNA at parS and non-specific DNA sites. ParB dimers interact with each other via flexible conformations of an N-terminal region. This review will focus on the properties of the HTH centromere-binding protein, in light of recent experimental evidence and models that are adding to our understanding of how these proteins assemble into large and dynamic partition complexes at and around their specific DNA sites. PMID:27622187

  15. ParB Partition Proteins: Complex Formation and Spreading at Bacterial and Plasmid Centromeres

    PubMed Central

    Funnell, Barbara E.

    2016-01-01

    In bacteria, active partition systems contribute to the faithful segregation of both chromosomes and low-copy-number plasmids. Each system depends on a site-specific DNA binding protein to recognize and assemble a partition complex at a centromere-like site, commonly called parS. Many plasmid, and all chromosomal centromere-binding proteins are dimeric helix-turn-helix DNA binding proteins, which are commonly named ParB. Although the overall sequence conservation among ParBs is not high, the proteins share similar domain and functional organization, and they assemble into similar higher-order complexes. In vivo, ParBs “spread,” that is, DNA binding extends away from the parS site into the surrounding non-specific DNA, a feature that reflects higher-order complex assembly. ParBs bridge and pair DNA at parS and non-specific DNA sites. ParB dimers interact with each other via flexible conformations of an N-terminal region. This review will focus on the properties of the HTH centromere-binding protein, in light of recent experimental evidence and models that are adding to our understanding of how these proteins assemble into large and dynamic partition complexes at and around their specific DNA sites.

  16. Proteinase-Activated Receptor 1 (PAR1) Regulates Leukemic Stem Cell Functions

    PubMed Central

    Bäumer, Nicole; Krause, Annika; Köhler, Gabriele; Lettermann, Stephanie; Evers, Georg; Hascher, Antje; Bäumer, Sebastian; Berdel, Wolfgang E.

    2014-01-01

    External signals that are mediated by specific receptors determine stem cell fate. The thrombin receptor PAR1 plays an important role in haemostasis, thrombosis and vascular biology, but also in tumor biology and angiogenesis. Its expression and function in hematopoietic stem cells is largely unknown. Here, we analyzed expression and function of PAR1 in primary hematopoietic cells and their leukemic counterparts. AML patients' blast cells expressed much lower levels of PAR1 mRNA and protein than CD34+ progenitor cells. Constitutive Par1-deficiency in adult mice did not affect engraftment or stem cell potential of hematopoietic cells. To model an AML with Par1-deficiency, we retrovirally introduced the oncogene MLL-AF9 in wild type and Par1−/− hematopoietic progenitor cells. Par1-deficiency did not alter initial leukemia development. However, the loss of Par1 enhanced leukemic stem cell function in vitro and in vivo. Re-expression of PAR1 in Par1−/− leukemic stem cells delayed leukemogenesis in vivo. These data indicate that Par1 contributes to leukemic stem cell maintenance. PMID:24740120

  17. ParB Partition Proteins: Complex Formation and Spreading at Bacterial and Plasmid Centromeres.

    PubMed

    Funnell, Barbara E

    2016-01-01

    In bacteria, active partition systems contribute to the faithful segregation of both chromosomes and low-copy-number plasmids. Each system depends on a site-specific DNA binding protein to recognize and assemble a partition complex at a centromere-like site, commonly called parS. Many plasmid, and all chromosomal centromere-binding proteins are dimeric helix-turn-helix DNA binding proteins, which are commonly named ParB. Although the overall sequence conservation among ParBs is not high, the proteins share similar domain and functional organization, and they assemble into similar higher-order complexes. In vivo, ParBs "spread," that is, DNA binding extends away from the parS site into the surrounding non-specific DNA, a feature that reflects higher-order complex assembly. ParBs bridge and pair DNA at parS and non-specific DNA sites. ParB dimers interact with each other via flexible conformations of an N-terminal region. This review will focus on the properties of the HTH centromere-binding protein, in light of recent experimental evidence and models that are adding to our understanding of how these proteins assemble into large and dynamic partition complexes at and around their specific DNA sites. PMID:27622187

  18. Dynamic Filament Formation by a Divergent Bacterial Actin-Like ParM Protein

    PubMed Central

    Brzoska, Anthony J.; Jensen, Slade O.; Barton, Deborah A.; Davies, Danielle S.; Overall, Robyn L.; Skurray, Ronald A.; Firth, Neville

    2016-01-01

    Actin-like proteins (Alps) are a diverse family of proteins whose genes are abundant in the chromosomes and mobile genetic elements of many bacteria. The low-copy-number staphylococcal multiresistance plasmid pSK41 encodes ParM, an Alp involved in efficient plasmid partitioning. pSK41 ParM has previously been shown to form filaments in vitro that are structurally dissimilar to those formed by other bacterial Alps. The mechanistic implications of these differences are not known. In order to gain insights into the properties and behavior of the pSK41 ParM Alp in vivo, we reconstituted the parMRC system in the ectopic rod-shaped host, E. coli, which is larger and more genetically amenable than the native host, Staphylococcus aureus. Fluorescence microscopy showed a functional fusion protein, ParM-YFP, formed straight filaments in vivo when expressed in isolation. Strikingly, however, in the presence of ParR and parC, ParM-YFP adopted a dramatically different structure, instead forming axial curved filaments. Time-lapse imaging and selective photobleaching experiments revealed that, in the presence of all components of the parMRC system, ParM-YFP filaments were dynamic in nature. Finally, molecular dissection of the parMRC operon revealed that all components of the system are essential for the generation of dynamic filaments. PMID:27310470

  19. The physical association of the P2Y12 receptor with PAR4 regulates arrestin-mediated Akt activation.

    PubMed

    Khan, Aasma; Li, Dongjun; Ibrahim, Salam; Smyth, Emer; Woulfe, Donna S

    2014-07-01

    It is now well accepted that protease activated receptor (PAR) 1 and PAR4 have differential roles in platelet activation. PAR4, a low-affinity thrombin receptor in human platelets, participates in sustained platelet activation in a P2Y12-dependent manner; however, the mechanisms are not defined. Our previous studies demonstrated that thrombin induces the association of PAR4 with P2Y12, together with arrestin recruitment to the complex. Here we show that PAR4 and P2Y12 directly interact to coregulate Akt signaling after PAR4 activation. We observed direct and specific interaction of P2Y12 with PAR4 but not PAR1 by bioluminescent resonance energy transfer when the receptors were coexpressed in human embryonic kidney 293T cells. PAR4-P2Y12 dimerization was promoted by PAR4-AP and inhibited by P2Y12 antagonist. By using sequence comparison of the transmembrane domains of PAR1 and PAR4, we designed a mutant form of PAR4, "PAR4SFT," by replacing LGL194-196 at the base of transmembrane domain 4 with the corresponding aligned PAR1 residues SFT 220-222. PAR4SFT supported only 8.74% of PAR4-P2Y12 interaction, abolishing P2Y12-dependent arrestin recruitment to PAR4 and Akt activation. Nonetheless, PAR4SFT still supported homodimerization with PAR4. PAR4SFT failed to induce a calcium flux when expressed independently; however, coexpression of increasing concentrations of PAR4SFT, together with PAR4 potentiated PAR4-mediated calcium flux, suggested that PAR4 act as homodimers to signal to Gq-coupled calcium responses. In conclusion, PAR4 LGL (194-196) governs agonist-dependent association of PAR4 with P2Y12 and contributes to Gq-coupled calcium responses. PAR4-P2Y12 association supports arrestin-mediated sustained signaling to Akt. Hence, PAR4-P2Y12 dimerization is likely to be important for the PAR4-P2Y12 dependent stabilization of platelet thrombi.

  20. The physical association of the P2Y12 receptor with PAR4 regulates arrestin-mediated Akt activation.

    PubMed

    Khan, Aasma; Li, Dongjun; Ibrahim, Salam; Smyth, Emer; Woulfe, Donna S

    2014-07-01

    It is now well accepted that protease activated receptor (PAR) 1 and PAR4 have differential roles in platelet activation. PAR4, a low-affinity thrombin receptor in human platelets, participates in sustained platelet activation in a P2Y12-dependent manner; however, the mechanisms are not defined. Our previous studies demonstrated that thrombin induces the association of PAR4 with P2Y12, together with arrestin recruitment to the complex. Here we show that PAR4 and P2Y12 directly interact to coregulate Akt signaling after PAR4 activation. We observed direct and specific interaction of P2Y12 with PAR4 but not PAR1 by bioluminescent resonance energy transfer when the receptors were coexpressed in human embryonic kidney 293T cells. PAR4-P2Y12 dimerization was promoted by PAR4-AP and inhibited by P2Y12 antagonist. By using sequence comparison of the transmembrane domains of PAR1 and PAR4, we designed a mutant form of PAR4, "PAR4SFT," by replacing LGL194-196 at the base of transmembrane domain 4 with the corresponding aligned PAR1 residues SFT 220-222. PAR4SFT supported only 8.74% of PAR4-P2Y12 interaction, abolishing P2Y12-dependent arrestin recruitment to PAR4 and Akt activation. Nonetheless, PAR4SFT still supported homodimerization with PAR4. PAR4SFT failed to induce a calcium flux when expressed independently; however, coexpression of increasing concentrations of PAR4SFT, together with PAR4 potentiated PAR4-mediated calcium flux, suggested that PAR4 act as homodimers to signal to Gq-coupled calcium responses. In conclusion, PAR4 LGL (194-196) governs agonist-dependent association of PAR4 with P2Y12 and contributes to Gq-coupled calcium responses. PAR4-P2Y12 association supports arrestin-mediated sustained signaling to Akt. Hence, PAR4-P2Y12 dimerization is likely to be important for the PAR4-P2Y12 dependent stabilization of platelet thrombi. PMID:24723492

  1. GABAergic inhibition regulates developmental synapse elimination in the cerebellum.

    PubMed

    Nakayama, Hisako; Miyazaki, Taisuke; Kitamura, Kazuo; Hashimoto, Kouichi; Yanagawa, Yuchio; Obata, Kunihiko; Sakimura, Kenji; Watanabe, Masahiko; Kano, Masanobu

    2012-04-26

    Functional neural circuit formation during development involves massive elimination of redundant synapses. In the cerebellum, one-to-one connection from excitatory climbing fiber (CF) to Purkinje cell (PC) is established by elimination of early-formed surplus CFs. This process depends on glutamatergic excitatory inputs, but contribution of GABAergic transmission remains unclear. Here, we demonstrate impaired CF synapse elimination in mouse models with diminished GABAergic transmission by mutation of a single allele for the GABA synthesizing enzyme GAD67, by conditional deletion of GAD67 from PCs and GABAergic interneurons or by pharmacological inhibition of cerebellar GAD activity. The impaired CF synapse elimination was rescued by enhancing GABA(A) receptor sensitivity in the cerebellum by locally applied diazepam. Our electrophysiological and Ca2+ imaging data suggest that GABA(A) receptor-mediated inhibition onto the PC soma from molecular layer interneurons influences CF-induced Ca2+ transients in the soma and regulates CF synapse elimination from postnatal day 10 (P10) to around P16. PMID:22542190

  2. Progress toward regional measles elimination--worldwide, 2000-2013.

    PubMed

    Perry, Robert T; Gacic-Dobo, Marta; Dabbagh, Alya; Mulders, Mick N; Strebel, Peter M; Okwo-Bele, Jean-Marie; Rota, Paul A; Goodson, James L

    2014-11-14

    In 2012, the World Health Assembly endorsed the Global Vaccine Action Plan with the objective to eliminate measles in four World Health Organization (WHO) regions by 2015. Member states of all six WHO regions have adopted measles elimination goals. In 2010, the World Health Assembly established three milestones for 2015: 1) increase routine coverage with the first dose of measles-containing vaccine (MCV1) for children aged 1 year to ≥90% nationally and ≥80% in every district; 2) reduce global annual measles incidence to <5 cases per million; and 3) reduce global measles mortality by 95% from the 2000 estimate. This report updates the 2000-2012 report and describes progress toward global control and regional measles elimination during 2000-2013. During this period, annual reported measles incidence declined 72% worldwide, from 146 to 40 per million population, and annual estimated measles deaths declined 75%, from 544,200 to 145,700. Four of six WHO regions have established regional verification commissions (RVCs); in the European (EUR) and Western Pacific regions (WPR), 19 member states successfully documented the absence of endemic measles. Resuming progress toward 2015 milestones and elimination goals will require countries and their partners to raise the visibility of measles elimination, address barriers to measles vaccination, and make substantial and sustained additional investments in strengthening health systems.

  3. Effective program management: a cornerstone of malaria elimination.

    PubMed

    Gosling, Jonathan; Case, Peter; Tulloch, Jim; Chandramohan, Daniel; Wegbreit, Jennifer; Newby, Gretchen; Gueye, Cara Smith; Koita, Kadiatou; Gosling, Roly

    2015-07-01

    Effective program management is essential for successful elimination of malaria. In this perspective article, evidence surrounding malaria program management is reviewed by management science and malaria experts through a literature search of published and unpublished gray documents and key informant interviews. Program management in a malaria elimination setting differs from that in a malaria control setting in a number of ways, although knowledge and understanding of these distinctions are lacking. Several core features of successful health program management are critical to achieve elimination, including effective leadership and supervision at all levels, sustained political and financial commitment, reliable supply and control of physical resources, effective management of data and information, appropriate incentives, and consistent accountability. Adding to the complexity, the requirements of an elimination program may conflict with those of a control regimen. Thus, an additional challenge is successfully managing program transitions along the continuum from control to elimination to prevention of reintroduction. This article identifies potential solutions to these challenges by exploring managerial approaches that are flexible, relevant, and sustainable in various cultural and health system contexts.

  4. Surveillance and response to drive the national malaria elimination program.

    PubMed

    Feng, Xin-Yu; Xia, Zhi-Gui; Vong, Sirenda; Yang, Wei-Zhong; Zhou, Shui-Sen

    2014-01-01

    The national action plan for malaria elimination in China (2010-2020) was issued by the Chinese Ministry of Health along with other 13 ministries and commissions in 2010. The ultimate goal of the national action plan was to eliminate local transmission of malaria by the end of 2020. Surveillance and response are the most important components driving the whole process of the national malaria elimination programme (NMEP), under the technical guidance used in NMEP. This chapter introduces the evolution of the surveillance from the control to the elimination stages and the current structure of national surveillance system in China. When the NMEP launched, both routine surveillance and sentinel surveillance played critical role in monitoring the process of NMEP. In addition, the current response strategy of NMEP was also reviewed, including the generally developed "1-3-7 Strategy". More effective and sensitive risk assessment tools were introduced, which cannot only predict the trends of malaria, but also are important for the design and adjustment of the surveillance and response systems in the malaria elimination stage. Therefore, this review presents the landscape of malaria surveillance and response in China as well as their contribution to the NMEP, with a focus on activities for early detection of malaria cases, timely control of malaria foci and epidemics, and risk prediction. Furthermore, challenges and recommendations for accelerating NMEP through surveillance are put forward. PMID:25476882

  5. Palladium catalyzed coupling reactions: mechanism of reductive elimination. Progress report, October 1, 1979-September 30, 1980. [Ethane elimination

    SciTech Connect

    Stille, J.K.

    1980-09-01

    The 1,1-reductive elimination of ethane from three cis-bis(phosphine)-dimethylpalladium complexes, L/sub 2/Pd(CH/sub 3/)/sub 2/ (L = PPh/sub 3/, PPh/sub 2/,CH/sub 3/ and L/sub 2/ = Ph/sub 2/PCH/sub 2/CH/sub 2/PPh/sub 2/), and three trans analogs (L = PPh/sub 3/, PPh/sub 2/CH/sub 3/ and L/sub 2/ = 2,11-bis(diphenylphosphinomethyl)benzo(c)phenanthrene (TRANSPHOS)) was carried out. The three cis complexes underwent reductive elimination in the presence of coordinating solvents (DMSO, DMF, and THF). The trans complexes which could isomerize to cis (L = PPh/sub 3/, PPh/sub 2/CH/sub 3/) did so in polar solvents and then underwent reductive elimination. TRANSPHOS dimethylpalladium would not undergo reductive elimination of ethane. The eliminations from the cis isomers were intramolecular and displayed first order kinetics. Although TRANSPHOS dimethylpalladium(II) would not undergo a 1,1-reductive elimination of ethane, the addition of CD/sub 3/I to a DMSO solution of this complex at 25/sup 0/C rapidly produced CD/sub 3/-CH/sub 3/, implicating a transient palladium(IV) intermediate. E- and Z-bromostyrylbis(diphenylmethylphosphine)palladium(0) react with methyl lithium in THF at ambient temperature to give the E- and Z- propenylbenzenes, respectively. At -78/sup 0/C, the intermediate E- and Z-styrylmethylbis(diphenylmethylphosphine)palladium(II) complexes (9a,b) can be isolated. On raising the temperature of solutions of 9a,b in THF, E- and Z-propenylbenzenes are produced. The reductive elimination reaction is intramolecular and first order in dialkylpalladium(II) complex.

  6. Collective cell migration requires suppression of actomyosin at cell-cell contacts mediated by DDR1 and the cell polarity regulators Par3 and Par6.

    PubMed

    Hidalgo-Carcedo, Cristina; Hooper, Steven; Chaudhry, Shahid I; Williamson, Peter; Harrington, Kevin; Leitinger, Birgit; Sahai, Erik

    2011-01-01

    Collective cell migration occurs in a range of contexts: cancer cells frequently invade in cohorts while retaining cell-cell junctions. Here we show that collective invasion by cancer cells depends on decreasing actomyosin contractility at sites of cell-cell contact. When actomyosin is not downregulated at cell-cell contacts, migrating cells lose cohesion. We provide a molecular mechanism for this downregulation. Depletion of discoidin domain receptor 1 (DDR1) blocks collective cancer-cell invasion in a range of two-dimensional, three-dimensional and 'organotypic' models. DDR1 coordinates the Par3/Par6 cell-polarity complex through its carboxy terminus, binding PDZ domains in Par3 and Par6. The DDR1-Par3/Par6 complex controls the localization of RhoE to cell-cell contacts, where it antagonizes ROCK-driven actomyosin contractility. Depletion of DDR1, Par3, Par6 or RhoE leads to increased actomyosin contactility at cell-cell contacts, a loss of cell-cell cohesion and defective collective cell invasion.

  7. ParABS Systems of the Four Replicons of Burkholderia cenocepacia: New Chromosome Centromeres Confer Partition Specificity†

    PubMed Central

    Dubarry, Nelly; Pasta, Franck; Lane, David

    2006-01-01

    Most bacterial chromosomes carry an analogue of the parABS systems that govern plasmid partition, but their role in chromosome partition is ambiguous. parABS systems might be particularly important for orderly segregation of multipartite genomes, where their role may thus be easier to evaluate. We have characterized parABS systems in Burkholderia cenocepacia, whose genome comprises three chromosomes and one low-copy-number plasmid. A single parAB locus and a set of ParB-binding (parS) centromere sites are located near the origin of each replicon. ParA and ParB of the longest chromosome are phylogenetically similar to analogues in other multichromosome and monochromosome bacteria but are distinct from those of smaller chromosomes. The latter form subgroups that correspond to the taxa of their hosts, indicating evolution from plasmids. The parS sites on the smaller chromosomes and the plasmid are similar to the “universal” parS of the main chromosome but with a sequence specific to their replicon. In an Escherichia coli plasmid stabilization test, each parAB exhibits partition activity only with the parS of its own replicon. Hence, parABS function is based on the independent partition of individual chromosomes rather than on a single communal system or network of interacting systems. Stabilization by the smaller chromosome and plasmid systems was enhanced by mutation of parS sites and a promoter internal to their parAB operons, suggesting autoregulatory mechanisms. The small chromosome ParBs were found to silence transcription, a property relevant to autoregulation. PMID:16452432

  8. Use of a static eliminator to improve powder flow.

    PubMed

    Pingali, Kalyana C; Hammond, Stephen V; Muzzio, Fernando J; Shinbrot, Troy

    2009-03-18

    Glidants and lubricants have long been used to improve the flow and processing of pharmaceutical and other powder blends. In this letter, we find that similar improvements can be attained, without additives, by using a simple static eliminator. These results indicate, first, that electrostatic effects on powder blends may be a significant cause of powder aggregation and flow instabilities, and second, that common additives such as magnesium stearate, colloidal silica, and talc may have as their chief effect the reduction of static. This suggests both that intelligent placement of static eliminators can eliminate the need for some of these additives and that judicious engineering of ionic and cationic additives may be effective in improving flow of "clingy" materials.

  9. Elimination kinetic model for organic chemicals in earthworms.

    PubMed

    Dimitrova, N; Dimitrov, S; Georgieva, D; Van Gestel, C A M; Hankard, P; Spurgeon, D; Li, H; Mekenyan, O

    2010-08-15

    Mechanistic understanding of bioaccumulation in different organisms and environments should take into account the influence of organism and chemical depending factors on the uptake and elimination kinetics of chemicals. Lipophilicity, metabolism, sorption (bioavailability) and biodegradation of chemicals are among the important factors that may significantly affect the bioaccumulation process in soil organisms. This study attempts to model elimination kinetics of organic chemicals in earthworms by accounting for the effects of both chemical and biological properties, including metabolism. The modeling approach that has been developed is based on the concept for simulating metabolism used in the BCF base-line model developed for predicting bioaccumulation in fish. Metabolism was explicitly accounted for by making use of the TIMES engine for simulation of metabolism and a set of principal transformations. Kinetic characteristics of transformations were estimated on the basis of observed kinetics data for the elimination of organic chemicals from earthworms. PMID:20185163

  10. Eliminating the Neglected Tropical Diseases: Translational Science and New Technologies

    PubMed Central

    Hotez, Peter J.; Pecoul, Bernard; Rijal, Suman; Boehme, Catharina; Aksoy, Serap; Malecela, Mwelecele; Tapia-Conyer, Roberto; Reeder, John C.

    2016-01-01

    Today, the World Health Organization recognizes 17 major parasitic and related infections as the neglected tropical diseases (NTDs). Despite recent gains in the understanding of the nature and prevalence of NTDs, as well as successes in recent scaled-up preventive chemotherapy strategies and other health interventions, the NTDs continue to rank among the world’s greatest global health problems. For virtually all of the NTDs (including those slated for elimination under the auspices of a 2012 London Declaration for NTDs and a 2013 World Health Assembly resolution [WHA 66.12]), additional control mechanisms and tools are needed, including new NTD drugs, vaccines, diagnostics, and vector control agents and strategies. Elimination will not be possible without these new tools. Here we summarize some of the key challenges in translational science to develop and introduce these new technologies in order to ensure success in global NTD elimination efforts. PMID:26934395

  11. Fast control latency uncertainty elimination for the BESIII ETOF upgrade

    NASA Astrophysics Data System (ADS)

    Wang, Yun; Cao, Ping; Liu, Shu-bin; An, Qi

    2016-09-01

    A new fanning topology is proposed to precisely fan out fast control signals in the Beijing Spectrometer (BESIII) end-cap time-of-flight (ETOF) electronics. However, uncertainty in transfer latency is introduced by the new fanning channel, which will degrade the precision of fast control. In this paper, latency uncertainty elimination for the BESIII ETOF upgrade is introduced. The latency uncertainty is determined by a Time-Digital-Converter (TDC) embedded in a Field-Programmable Gate Array (FPGA) and is eliminated by re-capturing at synchronous and determinate time. Compared with the existing method of Barrel-cap TOF (BTOF), it has advantages of flexible structure, easy calibration and good adaptability. Field tests on the BESIII ETOF system show that this method effectively eliminates transfer latency uncertainty. Supported by CAS Maintenance Project for Major Scientific and Technological Infrastructure (IHEP-SW-953/2013)

  12. Modeling Selective Elimination of Quiescent Cancer Cells from Bone Marrow

    PubMed Central

    Cavnar, Stephen P.; Rickelmann, Andrew D.; Meguiar, Kaille F.; Xiao, Annie; Dosch, Joseph; Leung, Brendan M.; Cai Lesher-Perez, Sasha; Chitta, Shashank; Luker, Kathryn E.; Takayama, Shuichi; Luker, Gary D.

    2015-01-01

    Patients with many types of malignancy commonly harbor quiescent disseminated tumor cells in bone marrow. These cells frequently resist chemotherapy and may persist for years before proliferating as recurrent metastases. To test for compounds that eliminate quiescent cancer cells, we established a new 384-well 3D spheroid model in which small numbers of cancer cells reversibly arrest in G1/G0 phase of the cell cycle when cultured with bone marrow stromal cells. Using dual-color bioluminescence imaging to selectively quantify viability of cancer and stromal cells in the same spheroid, we identified single compounds and combination treatments that preferentially eliminated quiescent breast cancer cells but not stromal cells. A treatment combination effective against malignant cells in spheroids also eliminated breast cancer cells from bone marrow in a mouse xenograft model. This research establishes a novel screening platform for therapies that selectively target quiescent tumor cells, facilitating identification of new drugs to prevent recurrent cancer. PMID:26408255

  13. Transcriptional Profiling of ParA and ParB Mutants in Actively Dividing Cells of an Opportunistic Human Pathogen Pseudomonas aeruginosa

    PubMed Central

    Bartosik, Aneta A.; Glabski, Krzysztof; Jecz, Paulina; Mikulska, Sylwia; Fogtman, Anna; Koblowska, Marta; Jagura-Burdzy, Grazyna

    2014-01-01

    Accurate chromosome segregation to progeny cells is a fundamental process ensuring proper inheritance of genetic material. In bacteria with simple cell cycle, chromosome segregation follows replication initiation since duplicated oriC domains start segregating to opposite halves of the cell soon after they are made. ParA and ParB proteins together with specific DNA sequences are parts of the segregation machinery. ParA and ParB proteins in Pseudomonas aeruginosa are important for optimal growth, nucleoid segregation, cell division and motility. Comparative transcriptome analysis of parAnull and parBnull mutants versus parental P. aeruginosa PAO1161 strain demonstrated global changes in gene expression pattern in logarithmically growing planktonic cultures. The set of genes similarly affected in both mutant strains is designated Par regulon and comprises 536 genes. The Par regulon includes genes controlled by two sigma factors (RpoN and PvdS) as well as known and putative transcriptional regulators. In the absence of Par proteins, a large number of genes from RpoS regulon is induced, reflecting the need for slowing down the cell growth rate and decelerating the metabolic processes. Changes in the expression profiles of genes involved in c-di-GMP turnover point out the role of this effector in such signal transmission. Microarray data for chosen genes were confirmed by RT-qPCR analysis. The promoter regions of selected genes were cloned upstream of the promoter-less lacZ gene and analyzed in the heterologous host E. coliΔlac. Regulation by ParA and ParB of P. aeruginosa was confirmed for some of the tested promoters. Our data demonstrate that ParA and ParB besides their role in accurate chromosome segregation may act as modulators of genes expression. Directly or indirectly, Par proteins are part of the wider regulatory network in P. aeruginosa linking the process of chromosome segregation with the cell growth, division and motility. PMID:24498062

  14. Is PAR a Good Investment? Understanding the Costs and Benefits of Teacher Peer Assistance and Review Programs

    ERIC Educational Resources Information Center

    Papay, John P.; Johnson, Susan Moore

    2012-01-01

    Peer Assistance and Review (PAR) is a local labor-management initiative designed to improve teacher quality. In PAR, expert "consulting teachers" mentor, support, and evaluate novice and underperforming veteran teachers. Evaluations under PAR can lead to dismissals. The authors examine the costs and benefits of PAR, both financial and…

  15. Traitement par plasma thermique d'une liqueur caustique pour la destruction des cyanures

    NASA Astrophysics Data System (ADS)

    Fortin, Luc

    L'objectif principal de cette recherche est d'evaluer la possibilite de traiter le lixiviat de brasques usees produit par le procede LCL&L (Lixiviation a bas caustique et chaulage) par contact direct avec un jet de plasma thermique. L'utilisation d'un chalumeau au plasma permet d'eliminer les problemes de reaction avec les produits de combustion relies a l'utilisation de chalumeaux conventionnels (e.g. carbonatation du NaOH en Na2CO3). Le fait de se servir de ce type de chalumeau en mode submerge pour le traitement d'une solution liquide constitue l'originalite du projet. Les essais effectues dans le cadre de ce travail experimental sont realises a l'echelle banc d'essai dans un premier temps. Ils visent a determiner le taux de decomposition des cyanures contenus dans le lixiviat sous des conditions de plasma thermique en fonction de differents parametres et a faire la mise a l'echelle d'un reacteur pilote. La puissance electrique fournie au chalumeau, la temperature et la pression d'operation, le point d'addition d'eau, le volume de lixiviat traite et l'addition de peroxyde d'hydrogene (H2O2) comme co-reactif ont tous un impact sur le taux de destruction des cyanures trouve. Sous toutes les conditions etudiees, le reacteur plasma offre un taux de destruction plus rapide qu'un reacteur agite sous pression pour une meme concentration en cyanures. Ainsi, la comparaison de la constante cinetique obtenue pour le reacteur agite avec une constante similaire pour le reacteur plasma (pente du graphique -ln(C/C0) en fonction du temps) est de 0.04x10-3 s-1 vs 0.59x10-3 s-1 a 100°C et de 1.85x10-3 s-1' vs 3x10 -3 s-1s a 170°C. Ces resultats confirment que le plasma joue un role important sur la decomposition des cyanures et qu'il contribue a en augmenter le taux de destruction. Suite aux connaissances acquises sur le banc d'essai, un reacteur pilote est concu. Un chalumeau au plasma d'une puissance de 60 kW-150 kW et fonctionnant avec l'air comme gaz plasmagene y est

  16. Élimination du bore du silicium par plasma inductif sous champ électrique

    NASA Astrophysics Data System (ADS)

    Combes, R.; Morvan, D.; Picard, G.; Amouroux, J.

    1993-05-01

    We analyzed purification mechanisms of silicon by inductive plasma with a fluoride slag. The aim is to study boron elimination from doped electronic grade silicon in function of the nature of the slag to obtain a photovoltaic grade silicon. The steady began with the calculation and the comparison of the stability diagram of boron compounds in presence of CaF2, BaF2 and MgF2. This study led us to conclude that BaF2 is the better slag for silicon purification. This has been confirmed by experience. In a second time, we made purifications under electric bias to enhance slag efficiency. We noticed that BaF2 is more sensitive to electric bias than other slags. Nous avons analysé le mécanisme de purification du silicium sous plasma inductif en présence d'un laitier fluoré. L'objectif principal est d'étudier l'élimination du bore du silicium électronique dopé en fonction de la nature du fluorure pour obtenir un silicium de qualité photovoltaïque. L'étude a commencé par l'établissement et la comparaison de diagrammes des composés du bore en présence de CaF2, de MgF2 et de BaF2. Nous avons déduit de cette première étude que BaF2 est le meilleur laitier pour la purification du silicium. Ceci a été corroboré par l'expérience. Nous avons ensuite opéré en présence d'un champ électrique dans le but d'améliorer encore l'efficacité des laitiers. Nous avons constaté que BaF2 est plus sensible au champ électrique que les deux autres laitiers utilisés.

  17. Identifying Malaria Transmission Foci for Elimination Using Human Mobility Data

    PubMed Central

    Ruktanonchai, Nick W.; DeLeenheer, Patrick; Tatem, Andrew J.; Alegana, Victor A.; Caughlin, T. Trevor; zu Erbach-Schoenberg, Elisabeth; Lourenço, Christopher; Ruktanonchai, Corrine W.; Smith, David L.

    2016-01-01

    Humans move frequently and tend to carry parasites among areas with endemic malaria and into areas where local transmission is unsustainable. Human-mediated parasite mobility can thus sustain parasite populations in areas where they would otherwise be absent. Data describing human mobility and malaria epidemiology can help classify landscapes into parasite demographic sources and sinks, ecological concepts that have parallels in malaria control discussions of transmission foci. By linking transmission to parasite flow, it is possible to stratify landscapes for malaria control and elimination, as sources are disproportionately important to the regional persistence of malaria parasites. Here, we identify putative malaria sources and sinks for pre-elimination Namibia using malaria parasite rate (PR) maps and call data records from mobile phones, using a steady-state analysis of a malaria transmission model to infer where infections most likely occurred. We also examined how the landscape of transmission and burden changed from the pre-elimination setting by comparing the location and extent of predicted pre-elimination transmission foci with modeled incidence for 2009. This comparison suggests that while transmission was spatially focal pre-elimination, the spatial distribution of cases changed as burden declined. The changing spatial distribution of burden could be due to importation, with cases focused around importation hotspots, or due to heterogeneous application of elimination effort. While this framework is an important step towards understanding progressive changes in malaria distribution and the role of subnational transmission dynamics in a policy-relevant way, future work should account for international parasite movement, utilize real time surveillance data, and relax the steady state assumption required by the presented model. PMID:27043913

  18. Determinants of Human African Trypanosomiasis Elimination via Paratransgenesis.

    PubMed

    Gilbert, Jennifer A; Medlock, Jan; Townsend, Jeffrey P; Aksoy, Serap; Ndeffo Mbah, Martial; Galvani, Alison P

    2016-03-01

    Human African trypanosomiasis (HAT), transmitted by tsetse flies, has historically infected hundreds of thousands of individuals annually in sub-Saharan Africa. Over the last decade, concerted control efforts have reduced reported cases to below 10,000 annually, bringing complete elimination within reach. A potential technology to eliminate HAT involves rendering the flies resistant to trypanosome infection. This approach can be achieved through the introduction of transgenic Sodalis symbiotic bacteria that have been modified to produce a trypanocide, and propagated via Wolbachia symbionts, which confer a reproductive advantage to the paratransgenic tsetse. However, the population dynamics of these symbionts within tsetse flies have not yet been evaluated. Specifically, the key factors that determine the effectiveness of paratransgenesis have yet to be quantified. To identify the impact of these determinants on T.b. gambiense and T.b. rhodesiense transmission, we developed a mathematical model of trypanosome transmission that incorporates tsetse and symbiont population dynamics. We found that fecundity and mortality penalties associated with Wolbachia or recombinant Sodalis colonization, probabilities of vertical transmission, and tsetse migration rates are fundamental to the feasibility of HAT elimination. For example, we determined that HAT elimination could be sustained over 25 years when Wolbachia colonization minimally impacted fecundity or mortality, and when the probability of recombinant Sodalis vertical transmission exceeded 99.9%. We also found that for a narrow range of recombinant Sodalis vertical transmission probability (99.9-90.6% for T.b. gambiense and 99.9-85.8% for T.b. rhodesiense), cumulative HAT incidence was reduced between 30% and 1% for T.b. gambiense and between 21% and 3% for T.b. rhodesiense, although elimination was not predicted. Our findings indicate that fitness and mortality penalties associated with paratransgenic symbionts, as well

  19. Identifying Malaria Transmission Foci for Elimination Using Human Mobility Data.

    PubMed

    Ruktanonchai, Nick W; DeLeenheer, Patrick; Tatem, Andrew J; Alegana, Victor A; Caughlin, T Trevor; Zu Erbach-Schoenberg, Elisabeth; Lourenço, Christopher; Ruktanonchai, Corrine W; Smith, David L

    2016-04-01

    Humans move frequently and tend to carry parasites among areas with endemic malaria and into areas where local transmission is unsustainable. Human-mediated parasite mobility can thus sustain parasite populations in areas where they would otherwise be absent. Data describing human mobility and malaria epidemiology can help classify landscapes into parasite demographic sources and sinks, ecological concepts that have parallels in malaria control discussions of transmission foci. By linking transmission to parasite flow, it is possible to stratify landscapes for malaria control and elimination, as sources are disproportionately important to the regional persistence of malaria parasites. Here, we identify putative malaria sources and sinks for pre-elimination Namibia using malaria parasite rate (PR) maps and call data records from mobile phones, using a steady-state analysis of a malaria transmission model to infer where infections most likely occurred. We also examined how the landscape of transmission and burden changed from the pre-elimination setting by comparing the location and extent of predicted pre-elimination transmission foci with modeled incidence for 2009. This comparison suggests that while transmission was spatially focal pre-elimination, the spatial distribution of cases changed as burden declined. The changing spatial distribution of burden could be due to importation, with cases focused around importation hotspots, or due to heterogeneous application of elimination effort. While this framework is an important step towards understanding progressive changes in malaria distribution and the role of subnational transmission dynamics in a policy-relevant way, future work should account for international parasite movement, utilize real time surveillance data, and relax the steady state assumption required by the presented model.

  20. Progress toward regional measles elimination - worldwide, 2000-2014.

    PubMed

    Perry, Robert T; Murray, Jillian S; Gacic-Dobo, Marta; Dabbagh, Alya; Mulders, Mick N; Strebel, Peter M; Okwo-Bele, Jean-Marie; Rota, Paul A; Goodson, James L

    2015-11-13

    In 2000, the United Nations General Assembly adopted the Millennium Development Goals (MDG), with MDG4 being a two-thirds reduction in child mortality by 2015, and with measles vaccination coverage being one of the three indicators of progress toward this goal.* In 2010, the World Health Assembly established three milestones for measles control by 2015: 1) increase routine coverage with the first dose of measles-containing vaccine (MCV1) for children aged 1 year to ≥90% nationally and ≥80% in every district; 2) reduce global annual measles incidence to fewer than five cases per million population; and 3) reduce global measles mortality by 95% from the 2000 estimate (1).† In 2012, the World Health Assembly endorsed the Global Vaccine Action Plan§ with the objective to eliminate measles in four World Health Organization (WHO) regions by 2015. WHO member states in all six WHO regions have adopted measles elimination goals. This report updates the 2000–2013 report (2) and describes progress toward global control and regional measles elimination during 2000–2014. During this period, annual reported measles incidence declined 73% worldwide, from 146 to 40 cases per million population, and annual estimated measles deaths declined 79%, from 546,800 to 114,900. However, progress toward the 2015 milestones and elimination goals has slowed markedly since 2010. To resume progress toward milestones and goals for measles elimination, a review of current strategies and challenges to improving program performance is needed, and countries and their partners need to raise the visibility of measles elimination, address barriers to measles vaccination, and make substantial and sustained additional investments in strengthening health systems. PMID:26562349

  1. Identifying Malaria Transmission Foci for Elimination Using Human Mobility Data.

    PubMed

    Ruktanonchai, Nick W; DeLeenheer, Patrick; Tatem, Andrew J; Alegana, Victor A; Caughlin, T Trevor; Zu Erbach-Schoenberg, Elisabeth; Lourenço, Christopher; Ruktanonchai, Corrine W; Smith, David L

    2016-04-01

    Humans move frequently and tend to carry parasites among areas with endemic malaria and into areas where local transmission is unsustainable. Human-mediated parasite mobility can thus sustain parasite populations in areas where they would otherwise be absent. Data describing human mobility and malaria epidemiology can help classify landscapes into parasite demographic sources and sinks, ecological concepts that have parallels in malaria control discussions of transmission foci. By linking transmission to parasite flow, it is possible to stratify landscapes for malaria control and elimination, as sources are disproportionately important to the regional persistence of malaria parasites. Here, we identify putative malaria sources and sinks for pre-elimination Namibia using malaria parasite rate (PR) maps and call data records from mobile phones, using a steady-state analysis of a malaria transmission model to infer where infections most likely occurred. We also examined how the landscape of transmission and burden changed from the pre-elimination setting by comparing the location and extent of predicted pre-elimination transmission foci with modeled incidence for 2009. This comparison suggests that while transmission was spatially focal pre-elimination, the spatial distribution of cases changed as burden declined. The changing spatial distribution of burden could be due to importation, with cases focused around importation hotspots, or due to heterogeneous application of elimination effort. While this framework is an important step towards understanding progressive changes in malaria distribution and the role of subnational transmission dynamics in a policy-relevant way, future work should account for international parasite movement, utilize real time surveillance data, and relax the steady state assumption required by the presented model. PMID:27043913

  2. Tissue distribution and elimination of rotenone in rainbow trout

    USGS Publications Warehouse

    Gingerich, W.H.

    1986-01-01

    The fate of a single i.v. dose (120 μg/kg) of the piscicide [14C]rotenone was evaluated in rainbow trout for periods up to 72 h after dosing. Rotenone was rapidly cleared from the plasma; less than 2% of the dose remained in the plasma compartment after 20 min. The highest concentrations of rotenone residues (% dose/g tissue) were in the hepatobiliary system, bile, intestine, and in heart, lateral line swimming muscle, and posterior kidney; tissues that are highly dependent on oxidative metabolism. Although rotenone activity was present in all cell fractions examined, greater than 40% was associated with the mitochondrial fraction of liver, kidney, and muscle. More than 85% of the activity extracted from these tissues, except the liver, was parent rotenone. Elimination from whole body and major tissue depots conformed to simple first-order kinetics; the estimated half-life from whole body was 68.5 h. Branchial elimination accounted for 5% of the injected dose over a 4-h period, and urinary elimination was less than 2% over a 48-h period. Rotenone was eliminated essentially unchanged across the gills; however, parent rotenone was not found in either urine or bile. More than 80% of the activity in both urine and bile eluted from HPLC chromatographs as a highly polar fraction that was not hydrolyzed by incubation with either β-glucuronidase or sulfatase. The results imply that hepatobiliary excretion is the major route of elimination for rotenone residues in the trout and that metabolism to a more polar form is a prerequisite for elimination in both the bile and the urine

  3. Determinants of Human African Trypanosomiasis Elimination via Paratransgenesis.

    PubMed

    Gilbert, Jennifer A; Medlock, Jan; Townsend, Jeffrey P; Aksoy, Serap; Ndeffo Mbah, Martial; Galvani, Alison P

    2016-03-01

    Human African trypanosomiasis (HAT), transmitted by tsetse flies, has historically infected hundreds of thousands of individuals annually in sub-Saharan Africa. Over the last decade, concerted control efforts have reduced reported cases to below 10,000 annually, bringing complete elimination within reach. A potential technology to eliminate HAT involves rendering the flies resistant to trypanosome infection. This approach can be achieved through the introduction of transgenic Sodalis symbiotic bacteria that have been modified to produce a trypanocide, and propagated via Wolbachia symbionts, which confer a reproductive advantage to the paratransgenic tsetse. However, the population dynamics of these symbionts within tsetse flies have not yet been evaluated. Specifically, the key factors that determine the effectiveness of paratransgenesis have yet to be quantified. To identify the impact of these determinants on T.b. gambiense and T.b. rhodesiense transmission, we developed a mathematical model of trypanosome transmission that incorporates tsetse and symbiont population dynamics. We found that fecundity and mortality penalties associated with Wolbachia or recombinant Sodalis colonization, probabilities of vertical transmission, and tsetse migration rates are fundamental to the feasibility of HAT elimination. For example, we determined that HAT elimination could be sustained over 25 years when Wolbachia colonization minimally impacted fecundity or mortality, and when the probability of recombinant Sodalis vertical transmission exceeded 99.9%. We also found that for a narrow range of recombinant Sodalis vertical transmission probability (99.9-90.6% for T.b. gambiense and 99.9-85.8% for T.b. rhodesiense), cumulative HAT incidence was reduced between 30% and 1% for T.b. gambiense and between 21% and 3% for T.b. rhodesiense, although elimination was not predicted. Our findings indicate that fitness and mortality penalties associated with paratransgenic symbionts, as well

  4. Progress toward regional measles elimination - worldwide, 2000-2014.

    PubMed

    Perry, Robert T; Murray, Jillian S; Gacic-Dobo, Marta; Dabbagh, Alya; Mulders, Mick N; Strebel, Peter M; Okwo-Bele, Jean-Marie; Rota, Paul A; Goodson, James L

    2015-11-13

    In 2000, the United Nations General Assembly adopted the Millennium Development Goals (MDG), with MDG4 being a two-thirds reduction in child mortality by 2015, and with measles vaccination coverage being one of the three indicators of progress toward this goal.* In 2010, the World Health Assembly established three milestones for measles control by 2015: 1) increase routine coverage with the first dose of measles-containing vaccine (MCV1) for children aged 1 year to ≥90% nationally and ≥80% in every district; 2) reduce global annual measles incidence to fewer than five cases per million population; and 3) reduce global measles mortality by 95% from the 2000 estimate (1).† In 2012, the World Health Assembly endorsed the Global Vaccine Action Plan§ with the objective to eliminate measles in four World Health Organization (WHO) regions by 2015. WHO member states in all six WHO regions have adopted measles elimination goals. This report updates the 2000–2013 report (2) and describes progress toward global control and regional measles elimination during 2000–2014. During this period, annual reported measles incidence declined 73% worldwide, from 146 to 40 cases per million population, and annual estimated measles deaths declined 79%, from 546,800 to 114,900. However, progress toward the 2015 milestones and elimination goals has slowed markedly since 2010. To resume progress toward milestones and goals for measles elimination, a review of current strategies and challenges to improving program performance is needed, and countries and their partners need to raise the visibility of measles elimination, address barriers to measles vaccination, and make substantial and sustained additional investments in strengthening health systems.

  5. Global control and regional elimination of measles, 2000-2012.

    PubMed

    Perry, Robert T; Gacic-Dobo, Marta; Dabbagh, Alya; Mulders, Mick N; Strebel, Peter M; Okwo-Bele, Jean-Marie; Rota, Paul A; Goodson, James L

    2014-02-01

    In 2010, the World Health Assembly established three milestones toward global measles eradication to be reached by 2015: 1) increase routine coverage with the first dose of measles-containing vaccine (MCV1) for children aged 1 year to ≥90% nationally and ≥80% in every district, 2) reduce and maintain annual measles incidence at <5 cases per million, and 3) reduce measles mortality by 95% from the 2000 estimate. After the adoption by member states of the South-East Asia Region (SEAR) of the goal of measles elimination by 2020, elimination goals have been set by member states of all six World Health Organization (WHO) regions, and reaching measles elimination in four WHO regions by 2015 is an objective of the Global Vaccine Action Plan (GVAP). This report updates the previous report for 2000-2011 and describes progress toward global control and regional elimination of measles during 2000-2012. During this period, increases in routine MCV coverage, plus supplementary immunization activities (SIAs) reaching 145 million children in 2012, led to a 77% decrease worldwide in reported measles annual incidence, from 146 to 33 per million population, and a 78% decline in estimated annual measles deaths, from 562,400 to 122,000. Compared with a scenario of no vaccination, an estimated 13.8 million deaths were prevented by measles vaccination during 2000-2012. Achieving the 2015 targets and elimination goals will require countries and their partners to raise the visibility of measles elimination and make substantial and sustained additional investments in strengthening health systems.

  6. Hepatic ethanol elimination kinetics in patients with cirrhosis

    PubMed Central

    DAM, GITTE; SØRENSEN, MICHAEL; MUNK, OLE LAJORD; KEIDING, SUSANNE

    2011-01-01

    Objective To address the question of whether increased ethanol elimination in alcoholics can be ascribed to increased metabolism via alcohol dehydrogenase (ADH; Km around 0.2 mM) or the microsomal ethanol-oxidizing system (MEOS; Km 10 mM) by kinetic analysis of hepatic ethanol elimination in recently drinking patients with alcoholic cirrhosis and healthy subjects. A further objective was to investigate whether systemic clearance of ethanol at low arterial ethanol concentrations can be used as a measure of hepatic blood flow. Material and methods Six patients with alcoholic cirrhosis were enrolled after 2 days of abstinence, along with 6 healthy subjects. Ethanol was administered as 6 successive infusions in increasing doses. Arterial and hepatic venous blood concentrations of ethanol were measured; hepatic blood flow was measured simultaneously. Kinetic parameters were calculated according to the sinusoidal perfusion model of enzymatic elimination by the intact liver. Results Mean hepatic Km for ethanol was 0.16 mM (range 0.09–0.36) in healthy subjects and 0.36 mM (range 0.16–0.69) in patients with cirrhosis (p>0.3), both compatible with the Km for ADH. The two groups of subjects had similar Vmax values (p>0.3). Extrahepatic elimination of ethanol accounted for more than 50% of total elimination in both groups, which precludes the use of systemic clearance as a measure of hepatic blood flow. Conclusions The results support the hypothesis that ADH remains the main pathway for hepatic elimination of ethanol in recently drinking patients with alcoholic cirrhosis. We interpret this as evidence against a significant contribution of MEOS in vivo. PMID:19404864

  7. Determinants of Human African Trypanosomiasis Elimination via Paratransgenesis

    PubMed Central

    Gilbert, Jennifer A.; Medlock, Jan; Townsend, Jeffrey P.; Aksoy, Serap

    2016-01-01

    Human African trypanosomiasis (HAT), transmitted by tsetse flies, has historically infected hundreds of thousands of individuals annually in sub-Saharan Africa. Over the last decade, concerted control efforts have reduced reported cases to below 10,000 annually, bringing complete elimination within reach. A potential technology to eliminate HAT involves rendering the flies resistant to trypanosome infection. This approach can be achieved through the introduction of transgenic Sodalis symbiotic bacteria that have been modified to produce a trypanocide, and propagated via Wolbachia symbionts, which confer a reproductive advantage to the paratransgenic tsetse. However, the population dynamics of these symbionts within tsetse flies have not yet been evaluated. Specifically, the key factors that determine the effectiveness of paratransgenesis have yet to be quantified. To identify the impact of these determinants on T.b. gambiense and T.b. rhodesiense transmission, we developed a mathematical model of trypanosome transmission that incorporates tsetse and symbiont population dynamics. We found that fecundity and mortality penalties associated with Wolbachia or recombinant Sodalis colonization, probabilities of vertical transmission, and tsetse migration rates are fundamental to the feasibility of HAT elimination. For example, we determined that HAT elimination could be sustained over 25 years when Wolbachia colonization minimally impacted fecundity or mortality, and when the probability of recombinant Sodalis vertical transmission exceeded 99.9%. We also found that for a narrow range of recombinant Sodalis vertical transmission probability (99.9–90.6% for T.b. gambiense and 99.9–85.8% for T.b. rhodesiense), cumulative HAT incidence was reduced between 30% and 1% for T.b. gambiense and between 21% and 3% for T.b. rhodesiense, although elimination was not predicted. Our findings indicate that fitness and mortality penalties associated with paratransgenic symbionts, as

  8. The elimination of building vibration in an optical laboratory.

    PubMed

    Slaymaker, F H

    1966-11-01

    The elimination of vibration is a straightforward engineering job that is analogous to the design of an electrical filter. The building vibration, which was so intense that no serious interferometry was possible, was measured using a commercial vibration meter. A simple, single-mesh mechanical filter was designed to remove the existing frequencies of vibration. The filter was constructed and its performance measured. As a practical test of the performance of the vibration elimination, a hologram was made on the vibration isolated granite slab.

  9. Helicobacter pylori Eradication to Eliminate Gastric Cancer: The Japanese Strategy.

    PubMed

    Asaka, Masahiro; Mabe, Katsuhiro; Matsushima, Rumiko; Tsuda, Momoko

    2015-09-01

    Helicobacter pylori eradication therapy for chronic gastritis achieved world-first coverage by the Japanese national health insurance scheme in 2013, making a dramatic decrease of gastric cancer-related deaths more realistic. Combining H pylori eradication therapy with endoscopic surveillance can prevent the development of gastric cancer. Even if it develops, most patients are likely to be diagnosed at an early stage, possibly resulting in fewer gastric cancer deaths. Success with the elimination of gastric cancer in Japan could lead other countries with a high incidence to consider a similar strategy, suggesting the potential for elimination of gastric cancer around the world.

  10. The elimination of building vibration in an optical laboratory.

    PubMed

    Slaymaker, F H

    1966-11-01

    The elimination of vibration is a straightforward engineering job that is analogous to the design of an electrical filter. The building vibration, which was so intense that no serious interferometry was possible, was measured using a commercial vibration meter. A simple, single-mesh mechanical filter was designed to remove the existing frequencies of vibration. The filter was constructed and its performance measured. As a practical test of the performance of the vibration elimination, a hologram was made on the vibration isolated granite slab. PMID:20057623

  11. Electrostatic mirror objective with eliminated spherical and axial chromatic aberrations.

    PubMed

    Bimurzaev, Seitkerim B; Serikbaeva, Gulnur S; Yakushev, Evgeniy M

    2003-01-01

    Computational formulae for the coefficients of the third-order spherical aberration and the second-order axial chromatic aberration are presented for an axially symmetric electrostatic electron mirror. A technique for eliminating the high-order derivatives of the potential axial distribution in mirror systems from the integrands is described. Conditions for elimination of spherical and axial chromatic aberrations, either separately or simultaneously, are found for a three-electrode axially symmetric mirror composed of coaxial cylinders of the same diameter. A principal scheme of the transmission electron microscope, where an electrostatic electron mirror serves as its objective, is presented. PMID:14599097

  12. A model for the condensation of the bacterial chromosome by the partitioning protein ParB

    NASA Astrophysics Data System (ADS)

    Broedersz, Chase; Wingreen, Ned

    2013-03-01

    The molecular machinery responsible for faithful segregation of the chromosome in bacteria such as Caulobacter crescentus and Bacillus subtilis includes the ParABS a.k.a. Spo0J/Soj partitioning system. In Caulobacter, prior to division, hundreds of ParB proteins bind to the DNA near the origin of replication, and localize to one pole of the cell. Subsequently, the ParB-DNA complex is translocated to the far pole by the binding and retraction of the ParA spindle-like apparatus. Remarkably, the localization of ParB proteins to specific regions of the chromosome appears to be controlled by only a few centromeric parS binding sites. Although lateral interactions between DNA-bound ParB are likely to be important for their localization, the long-range order of ParB domains on the chromosome appears to be inconsistent with a picture in which protein-protein interactions are limited to neighboring DNA-bound proteins. We developed a coarse-grained Brownian dynamics model that allows for lateral and 3D protein-protein interactions among bound ParB proteins. Our model shows how such interactions can condense and organize the DNA spatially, and can control the localization and the long-range order of the DNA-bound proteins.

  13. An ELISA method detecting the active form of suPAR.

    PubMed

    Zhou, Xiaolei; Xu, Mingming; Huang, Hailong; Mazar, Andrew; Iqbal, Zafar; Yuan, Cai; Huang, Mingdong

    2016-11-01

    Urokinase plasminogen activator receptor (uPAR) exists in a number of formats in human plasma, including soluble uPAR (suPAR) and uPAR fragments. We developed an ELISA method to detect specifically the active form suPAR, which binds to its natural ligand uPA. The intra CV and inter CV of this ELISA assay is 8.5% and 9.6% respectively, and the assay can recover 99.74% of added recombinant suPAR from 10% plasma. This assay is quite sensitive, capable of detecting down to 15pg/ml of suPAR, and can measure suPAR concentrations in the range of 0.031-8ng/ml with high linear relationship. Plasma samples from pregnant women were also measured for the active form of suPAR with this assay, giving an averaged level of 1.39ng/ml, slightly higher than the level of pooled plasma from healthy donors (0.96ng/ml). This study demonstrates the feasibility to measure the active form of suPAR, which will likely have value in clinical applications. PMID:27591605

  14. Serum suPAR in patients with FSGS: trash or treasure?

    PubMed

    Maas, Rutger J H; Deegens, Jeroen K J; Wetzels, Jack F M

    2013-07-01

    The urokinase-type plasminogen activator receptor (uPAR) has important functions in cell migration. uPAR can be shed from the cell membrane resulting in soluble uPAR (suPAR). Further cleavage gives rise to shorter fragments with largely unknown functions. Recent studies have demonstrated that both overexpression of uPAR on podocytes and the administration of suPAR cause proteinuria in mice. The common pathogenic mechanism involves the activation of podocyte β3-integrin. Increased activation of β3-integrin is also observed in patients with focal and segmental glomerulosclerosis (FSGS). These observations form the basis for the hypothesis that suPAR may be the circulating factor causing FSGS. A recent study fosters this idea by demonstrating increased suPAR levels in the serum of patients with FSGS and reporting an association with recurrence after transplantation and response to plasmapheresis. However, this study was heavily biased, and subsequent studies have given conflicting results. Although the experimental work is very suggestive, at present there is no proof that any known human suPAR fragment causes FSGS in humans. We therefore suggest that the measurement of suPAR using currently available assays has absolutely no value at the present time in decision-making in routine clinical practice.

  15. Décontamination nucléaire par laser UV

    NASA Astrophysics Data System (ADS)

    Delaporte, Ph.; Gastaud, M.; Marine, W.; Sentis, M.; Uteza, O.; Thouvenot, P.; Alcaraz, J. L.; Le Samedy, J. M.; Blin, D.

    2003-06-01

    Le développement et l'utilisation de procédés propres pour le nettoyage ou la préparation de surfaces est l'une des priorités du milieu industriel. Cet intérêt est d'autant plus grand dans le domaine du nucléaire pour lequel la réduction des déchets est un axe de recherche important. Un dispositif de décontamination nucléaire par laser UV impulsionnel a été développé et testé. Il est composé. d'un laser à excimères de 1kW, d'un faisceau de fibres optiques et d'un dispositif de récupération des particules. Les essais réalisés en milieu actif ont démontré sa capacité à nettoyer des surfaces métalliques polluées par différents radioéléments avec des facteurs de décontamination généralement supérieurs à 10. Ce dispositif permet de décontaminer de grandes surfaces de géométrie simple en réduisant fortement la génération de déchets secondaires. Il est, à ce jour et dans ces conditions d'utilisations, le procédé de décontamination par voie sèche le plus efficace.

  16. Kinetic studies of the reverse reaction catalysed by adenosine triphosphate–creatine phosphotransferase. The inhibition by magnesium ions and adenosine diphosphate

    PubMed Central

    Morrison, J. F.; O'Sullivan, W. J.

    1965-01-01

    1. Kinetic investigations of the reaction catalysed by ATP–creatine phosphotransferase have been carried out. 2. No firm conclusions could be reached about the reaction of Mg2+ at the nucleotide-binding site of the enzyme. The value of the kinetic constant for this reaction depends on the value used for the apparent stability constant of the metal ion–nucleotide complex and, to a smaller extent, on the method of plotting the results. 3. At higher concentrations Mg2+ is a non-competitive inhibitor of the enzyme with respect to both MgADP− and phosphocreatine. 4. ADP3− is a competitive inhibitor of the enzyme with respect to MgADP− and a non-competitive inhibitor with respect to phosphocreatine. 5. The concentration of phosphocreatine has little, if any, effect on the kinetic constants for the nucleotide reactants. PMID:14342234

  17. Determination of phenol by flow-injection with chemiluminescence detection based on the hemin-catalysed luminol-hydrogen peroxide reaction

    NASA Astrophysics Data System (ADS)

    Liu, Wenwen; Cao, Wei; Liu, Weihua; Du, Kang; Gong, Pixue

    2012-01-01

    This study established a novel flow injection (FI) methodology for the determination of phenol in aqueous samples based on luminol chemiluminescence (CL) detection. The method was based on the inhibition that phenol caused on the hemin-catalysed chemiluminescence reaction between luminol and hydrogen peroxide in alkaline solution. Optimum conditions and possible mechanisms have been investigated. The linear range was 2.0 × 10 -9 to 4.0 × 10 -7 g mL -1 for phenol. The proposed method is sensitive with a detection limit of 4.0 × 10 -10 g mL -1. The relative standard deviation for 11 measurements was 2.3% for 1.0 × 10 -7g mL -1 phenol. The method was applied for the determination of phenol in waste water samples. The results obtained compared well with those by an official method.

  18. Rhodium-catalysed C(sp2)–C(sp2) bond formation via C–H/C–F activation

    PubMed Central

    Tian, Panpan; Feng, Chao; Loh, Teck-Peng

    2015-01-01

    Fluoroalkenes represent a class of privileged structural motifs, which found widespread use in medicinal chemistry. However, the synthetic access to fluoroalkenes was much underdeveloped with previous reported methods suffering from either low step economy or harsh reaction conditions. Here we present a RhIII-catalysed tandem C–H/C–F activation for the synthesis of (hetero)arylated monofluoroalkenes. The use of readily available gem-difluoroalkenes as electrophiles provides a highly efficient and operationally simple method for the introduction of α-fluoroalkenyl motifs onto (hetero)arenes under oxidant-free conditions. Furthermore, the employment of alcoholic solvent and the in-situ generated hydrogen fluoride are found to be beneficial in this transformation, indicating the possibility of the involvement of hydrogen bond activation mode with regards to the C–F bond cleavage step. PMID:26081837

  19. Heterogeneous Cu(II) -catalysed solvent-controlled selective N-arylation of cyclic amides and amines with bromo-iodoarenes.

    PubMed

    Kundu, Debasish; Bhadra, Sukalyan; Mukherjee, Nirmalya; Sreedhar, Bojja; Ranu, Brindaban C

    2013-11-11

    A selective N-arylation of cyclic amides and amines in DMF and water, respectively, catalysed by Cu(II) /Al2 O3 has been achieved. This protocol has been employed for the synthesis of a library of arenes bearing a cyclic amide and an amine moiety at two ends, including a few scaffolds of therapeutic importance. The mechanism has been established based on detailed electron paramagnetic resonance (EPR) spectroscopy, X-ray photoelectron spectroscopy (XPS), UV diffuse reflectance spectroscopy (DRS) and inductively coupled plasma-mass spectrometry (ICP-MS) studies of the catalyst at different stages of the reaction. The Cu(II) /Al2 O3 catalyst was recovered and recycled for subsequent reactions. PMID:24123356

  20. Flow-injection stopped-flow kinetic spectrophotometric determination of drugs, based on micellar-catalysed reaction with 1-fluoro-2,4-dinitrobenzene.

    PubMed

    Georgiou, C A; Koupparis, M A; Hadjiioannou, T P

    1991-07-01

    A flow-injection stopped-flow kinetic spectrophotometric method for the determination of hydrazines, hydrazides, amines and amino-acids, based on the cetyltrimethylammonium bromide catalysed reaction with 1-fluoro-2,4-dinitrobenzene is described. With the proposed method dihydralazine, isoniazid, levodopa and aspartame can be determined at concentrations of 0.1-6 x 10(-4)M. The calibration ranges can be varied by adjusting the pH and surfactant concentration. The determination of amphetamine, cysteine, s-carboxymethylcysteine, cephalexin, tobramycin and gentamicin is also feasible. The method has been applied to the determination of levodopa, isoniazid and aspartame in commercial pharmaceutical formulations. The determination of isoniazid in formulations containing the highly coloured antibiotic rifamycin, and of aspartame in coloured beverages was also accomplished. The results were in good agreement with those obtained by reference methods and the throughput was 40 measurements per hour with 0.4-3.9% RSD.