Sample records for efficient partial synthesis

  1. Thermally efficient melting and fuel reforming for glass making

    DOEpatents

    Chen, Michael S.; Painter, Corning F.; Pastore, Steven P.; Roth, Gary S.; Winchester, David C.

    1991-01-01

    An integrated process for utilizing waste heat from a glass making furnace. The hot off-gas from the furnace is initially partially cooled, then fed to a reformer. In the reformer, the partially cooled off-gas is further cooled against a hydrocarbon which is thus reformed into a synthesis gas, which is then fed into the glass making furnace as a fuel. The further cooled off-gas is then recycled back to absorb the heat from the hot off-gas to perform the initial cooling.

  2. Au-HKUST-1 Composite Nanocapsules: Synthesis with a Coordination Replication Strategy and Catalysis on CO Oxidation.

    PubMed

    Liu, Yongxin; Zhang, Jiali; Song, Lingxiao; Xu, Wenyuan; Guo, Zanru; Yang, Xiaomin; Wu, Xiaoxin; Chen, Xi

    2016-09-07

    A novel coordination replication of Cu2O redox-template strategy is reported to efficiently fabricate Au-HKUST-1 composite nanocapsule, with a HKUST-1 sandwich shell and an embedded Au nanoparticles layer. The novel synthesis procedure involves forming Au nanoparticles on the surface of Cu2O, transforming partial Cu2O into HKUST-1 shell via coordination replication, and removing the residual Cu2O by acid. The as-prepared Au-HKUST-1 composite nanocapsules displayed high catalytic activity on CO oxidation.

  3. Thermally efficient melting and fuel reforming for glass making

    DOEpatents

    Chen, M.S.; Painter, C.F.; Pastore, S.P.; Roth, G.S.; Winchester, D.C.

    1991-10-15

    An integrated process is described for utilizing waste heat from a glass making furnace. The hot off-gas from the furnace is initially partially cooled, then fed to a reformer. In the reformer, the partially cooled off-gas is further cooled against a hydrocarbon which is thus reformed into a synthesis gas, which is then fed into the glass making furnace as a fuel. The further cooled off-gas is then recycled back to absorb the heat from the hot off-gas to perform the initial cooling. 2 figures.

  4. Cyclic azole-homologated peptides from Marine sponges.

    PubMed

    Molinski, Tadeusz F

    2017-12-19

    This review discusses the chemistry of cyclic azole-homologated peptides (AHPs) from the marine sponges, Theonella swinhoei, other Theonella species, Calyx spp. and Plakina jamaicensis. The origin, distribution of AHPs and molecular structure elucidations of AHPs are described followed by their biosynthesis, bioactivity, and synthetic efforts towards their total synthesis. Reports of partial and total synthesis of AHPs extend beyond peptide coupling reactions and include creative construction of the non-proteinogenic amino acid components, mainly the homologated heteroaromatic and α-keto-β-amino acids. A useful conclusion is drawn regarding AHPs: despite their rarity, exotic structures and the potent protease inhibitory properties of some members, their synthesis is under-developed and beckons solutions for outstanding problems towards their efficient assembly.

  5. Partial oxidation of methane by pulsed corona discharges

    NASA Astrophysics Data System (ADS)

    Hoeben, W. F. L. M.; Boekhoven, W.; Beckers, F. J. C. M.; van Heesch, E. J. M.; Pemen, A. J. M.

    2014-09-01

    Pulsed corona-induced partial oxidation of methane in humid oxygen or carbon dioxide atmospheres has been investigated for future fuel synthesis applications. The obtained product spectrum is wide, i.e. saturated, unsaturated and oxygen-functional hydrocarbons. The generally observed methane conversion levels are 6-20% at a conversion efficiency of about 100-250 nmol J-1. The main products are ethane, ethylene and acetylene. Higher saturated hydrocarbons up to C6 have been detected. The observed oxygen-functional hydrocarbons are methanol, ethanol and lower concentrations of aldehydes, ketones, dimethylether and methylformate. Methanol seems to be exclusively produced with CH4/O2 mixtures at a maximum production efficiency of 0.35 nmol J-1. CH4/CO2 mixtures appear to yield higher hydrocarbons. Carboxylic acids appear to be mainly present in the aqueous reactor phase, possibly together with higher molecular weight species.

  6. The effect of growth temperature variation on partially bismuth filled carbon nanotubes synthesis using a soft semi-metallic template.

    PubMed

    Sahoo, R K; Jacob, C

    2014-06-01

    The dewetting of a low melting point metal thin film deposited on silicon substrates was studied. The experimental results suggest that the change in the growth temperature affects the nanostructures that form. Based on the experimental results, the temperature which yielded the smallest features for the growth of nanotubes is determined. The mechanism by which these nano-templates become an efficient seeds for the growth of the carbon nanotubes is discussed. The partial bismuth filling inside the CNTs was optimized. Based on the results, a schematic growth model for better understanding of the process parameters has also been proposed.

  7. Template-switching during DNA synthesis by Thermus aquaticus DNA polymerase I.

    PubMed Central

    Odelberg, S J; Weiss, R B; Hata, A; White, R

    1995-01-01

    Recombinant DNA molecules are often generated during the polymerase chain reaction (PCR) when partially homologous templates are available [e.g., see Pääbo et al. (1990) J. Biol. Chem. 265, 4718-4721]. It has been suggested that these recombinant molecules are a consequence of truncated extension products annealing to partially homologous templates on subsequent PCR cycles. However, we demonstrate here that recombinants can be generated during a single round of primer extension in the absence of subsequent heat denaturation, indicating that template-switching produces some of these recombinant molecules. Two types of template-switches were observed: (i) switches to pre-existing templates and (ii) switches to the complementary nascent strand. Recombination is reduced several fold when the complementary template strands are physically separated by attachment to streptavidin magnetic beads. This result supports the hypothesis that either the polymerase or at least one of the two extending strands switches templates during DNA synthesis and that interaction between the complementary template strands is necessary for efficient template-switching. Images PMID:7596836

  8. Partially oxidized iridium clusters within dendrimers: size-controlled synthesis and selective hydrogenation of 2-nitrobenzaldehyde

    NASA Astrophysics Data System (ADS)

    Higaki, Tatsuya; Kitazawa, Hirokazu; Yamazoe, Seiji; Tsukuda, Tatsuya

    2016-06-01

    Iridium clusters nominally composed of 15, 30 or 60 atoms were size-selectively synthesized within OH-terminated poly(amidoamine) dendrimers of generation 6. Spectroscopic characterization revealed that the Ir clusters were partially oxidized. All the Ir clusters efficiently converted 2-nitrobenzaldehyde to anthranil and 2-aminobenzaldehyde under atmospheric hydrogen at room temperature in toluene via selective hydrogenation of the NO2 group. The selectivity toward 2-aminobenzaldehyde over anthranil was improved with the reduction of the cluster size. The improved selectivity is ascribed to more efficient reduction than intramolecular heterocyclization of a hydroxylamine intermediate on smaller clusters that have a higher Ir(0)-phase population on the surface.Iridium clusters nominally composed of 15, 30 or 60 atoms were size-selectively synthesized within OH-terminated poly(amidoamine) dendrimers of generation 6. Spectroscopic characterization revealed that the Ir clusters were partially oxidized. All the Ir clusters efficiently converted 2-nitrobenzaldehyde to anthranil and 2-aminobenzaldehyde under atmospheric hydrogen at room temperature in toluene via selective hydrogenation of the NO2 group. The selectivity toward 2-aminobenzaldehyde over anthranil was improved with the reduction of the cluster size. The improved selectivity is ascribed to more efficient reduction than intramolecular heterocyclization of a hydroxylamine intermediate on smaller clusters that have a higher Ir(0)-phase population on the surface. Electronic supplementary information (ESI) available. See DOI: 10.1039/c6nr01460g

  9. Dissecting limiting factors of the Protein synthesis Using Recombinant Elements (PURE) system

    PubMed Central

    Li, Jun; Zhang, Chi; Huang, Poyi; Kuru, Erkin; Forster-Benson, Eliot T. C.; Church, George M.

    2017-01-01

    ABSTRACT Reconstituted cell-free protein synthesis systems such as the Protein synthesis Using Recombinant Elements (PURE) system give high-throughput and controlled access to in vitro protein synthesis. Here we show that compared with the commercial S30 crude extract based RTS 100 E. coli HY system, the PURE system has less mRNA degradation and produces up to ∼6-fold full-length proteins. However the majority of polypeptides PURE produces are partially translated or inactive since the signal from firefly luciferase (Fluc) translated in PURE is only ∼2/3rd of that measured using the RTS 100 E. coli HY S30 system. Both of the 2 batch systems suffer from low ribosome recycling efficiency when translating proteins from 82 kD to 224 kD. A systematic fed-batch analysis of PURE shows replenishment of 6 small molecule substrates individually or in combination before energy depletion increased Fluc protein yield by ∼1.5 to ∼2-fold, while creatine phosphate and magnesium have synergistic effects when added to the PURE system. Additionally, while adding EF-P to PURE reduced full-length protein translated, it increased the fraction of functional protein and reduced partially translated protein probably by slowing down the translation process. Finally, ArfA, rather than YaeJ or PrfH, helped reduce ribosome stalling when translating Fluc and improved system productivity in a template-dependent fashion. PMID:28702280

  10. Gold Nanoparticle Microwave Synthesis

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

    Krantz, Kelsie E.; Christian, Jonathan H.; Coopersmith, Kaitlin

    At the nanometer scale, numerous compounds display different properties than those found in bulk material that can prove useful in areas such as medicinal chemistry. Gold nanoparticles, for example, display promise in newly developed hyperthermia therapies for cancer treatment. Currently, gold nanoparticle synthesis is performed via the hot injection technique which has large variability in final particle size and a longer reaction time. One underdeveloped area by which these particles could be produced is through microwave synthesis. To initiate heating, microwaves agitate polar molecules creating a vibration that gives off the heat energy needed. Previous studies have used microwaves formore » gold nanoparticle synthesis; however, polar solvents were used that partially absorbed incident microwaves, leading to partial thermal heating of the sample rather than taking full advantage of the microwave to solely heat the gold nanoparticle precursors in a non-polar solution. Through this project, microwaves were utilized as the sole heat source, and non-polar solvents were used to explore the effects of microwave heating only as pertains to the precursor material. Our findings show that the use of non-polar solvents allows for more rapid heating as compared to polar solvents, and a reduction in reaction time from 10 minutes to 1 minute; this maximizes the efficiency of the reaction, and allows for reproducibility in the size/shape of the fabricated nanoparticles.« less

  11. Dissecting limiting factors of the Protein synthesis Using Recombinant Elements (PURE) system

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

    Li, Jun; Zhang, Chi; Huang, Poyi

    Reconstituted cell-free protein synthesis systems such as the Protein synthesis Using Recombinant Elements (PURE) system give high-throughput and controlled access to in vitro protein synthesis. Here we show that compared with the commercial S30 crude extract based RTS 100 E. coli HY system, the PURE system has less mRNA degradation and produces up to ~6-fold full-length proteins. However the majority of polypeptides PURE produces are partially translated or inactive since the signal from firefly luciferase (Fluc) translated in PURE is only ~2/3 rd of that measured using the RTS 100 E. coli HY S30 system. Both of the 2 batchmore » systems suffer from low ribosome recycling efficiency when translating proteins from 82 k D to 224 k D. A systematic fed-batch analysis of PURE shows replenishment of 6 small molecule substrates individually or in combination before energy depletion increased Fluc protein yield by ~1.5 to ~2-fold, while creatine phosphate and magnesium have synergistic effects when added to the PURE system. Additionally, while adding EF-P to PURE reduced full-length protein translated, it increased the fraction of functional protein and reduced partially translated protein probably by slowing down the translation process. Finally, ArfA, rather than YaeJ or PrfH, helped reduce ribosome stalling when translating Fluc and improved system productivity in a template-dependent fashion.« less

  12. Dissecting limiting factors of the Protein synthesis Using Recombinant Elements (PURE) system

    DOE PAGES

    Li, Jun; Zhang, Chi; Huang, Poyi; ...

    2017-05-09

    Reconstituted cell-free protein synthesis systems such as the Protein synthesis Using Recombinant Elements (PURE) system give high-throughput and controlled access to in vitro protein synthesis. Here we show that compared with the commercial S30 crude extract based RTS 100 E. coli HY system, the PURE system has less mRNA degradation and produces up to ~6-fold full-length proteins. However the majority of polypeptides PURE produces are partially translated or inactive since the signal from firefly luciferase (Fluc) translated in PURE is only ~2/3 rd of that measured using the RTS 100 E. coli HY S30 system. Both of the 2 batchmore » systems suffer from low ribosome recycling efficiency when translating proteins from 82 k D to 224 k D. A systematic fed-batch analysis of PURE shows replenishment of 6 small molecule substrates individually or in combination before energy depletion increased Fluc protein yield by ~1.5 to ~2-fold, while creatine phosphate and magnesium have synergistic effects when added to the PURE system. Additionally, while adding EF-P to PURE reduced full-length protein translated, it increased the fraction of functional protein and reduced partially translated protein probably by slowing down the translation process. Finally, ArfA, rather than YaeJ or PrfH, helped reduce ribosome stalling when translating Fluc and improved system productivity in a template-dependent fashion.« less

  13. Application of 2-chlorotrityl resin in solid phase synthesis of (Leu15)-gastrin I and unsulfated cholecystokinin octapeptide. Selective O-deprotection of tyrosine.

    PubMed

    Barlos, K; Gatos, D; Kapolos, S; Poulos, C; Schäfer, W; Yao, W Q

    1991-12-01

    The carboxyl terminal dipeptide amide, Fmoc-Asp-Phe-NH2, of gastrin and cholecystokinin (CCK) has been attached in high yield through its free side chain carboxyl group to the acid labile 2-chlorotrityl resin. The obtained peptide resin ester has been applied in the solid phase synthesis of partially protected (Leu15)-gastrin I utilising Fmoc-amino acids. Quantitative cleavage of this peptide from resin, with the t-butyl type side chain protection intact is achieved using mixtures of acetic acid/trifluoroethanol/dichloromethane. Under the same conditions complete detritylation of the tyrosine phenoxy function occurs simultaneously. Thus, the solid-phase synthesis of peptides selectively deprotected at the side chain of tyrosine is rendered possible by the use of 2-chlorotrityl resin and Fmoc-Tyr(Trt)-OH. The efficiency of this approach has been proved by the subsequent high-yield synthesis of three model peptides and the CCK-octapeptide.

  14. Efficient Mutagenesis Independent of Ligation (EMILI).

    PubMed

    Füzik, Tibor; Ulbrich, Pavel; Ruml, Tomáš

    2014-11-01

    Site-directed mutagenesis is one of the most widely used techniques in life sciences. Here we describe an improved and simplified method for introducing mutations at desired sites. It consists of an inverse PCR using a plasmid template and two partially complementary primers. The synthesis step is followed by annealing of the PCR product's sticky ends, which are generated by exonuclease digestion. This method is fast, extremely efficient and cost-effective. It can be used to introduce large insertions and deletions, but also for multiple point mutations in a single step. To show the principle and to prove the efficiency of the method, we present a series of basic mutations (insertions, deletions, point mutations) on pUC19 plasmid DNA. Copyright © 2014 Elsevier B.V. All rights reserved.

  15. A Tomato Peroxidase Involved in the Synthesis of Lignin and Suberin1

    PubMed Central

    Quiroga, Mónica; Guerrero, Consuelo; Botella, Miguel A.; Barceló, Araceli; Amaya, Iraida; Medina, María I.; Alonso, Francisco J.; de Forchetti, Silvia Milrad; Tigier, Horacio; Valpuesta, Victoriano

    2000-01-01

    The last step in the synthesis of lignin and suberin has been proposed to be catalyzed by peroxidases, although other proteins may also be involved. To determine which peroxidases are involved in the synthesis of lignin and suberin, five peroxidases from tomato (Lycopersicon esculentum) roots, representing the majority of the peroxidase activity in this organ, have been partially purified and characterized kinetically. The purified peroxidases with isoelectric point (pI) values of 3.6 and 9.6 showed the highest catalytic efficiency when the substrate used was syringaldazine, an analog of lignin monomer. Using a combination of transgenic expression and antibody recognition, we now show that the peroxidase pI 9.6 is probably encoded by TPX1, a tomato peroxidase gene we have previously isolated. In situ RNA hybridization revealed that TPX1 expression is restricted to cells undergoing synthesis of lignin and suberin. Salt stress has been reported to induce the synthesis of lignin and/or suberin. This stress applied to tomato caused changes in the expression pattern of TPX1 and induced the TPX1 protein. We propose that the TPX1 product is involved in the synthesis of lignin and suberin. PMID:10759507

  16. Physiological responses to digestion in low salinity in the crabs Carcinus maenas and Cancer irroratus.

    PubMed

    Penney, Chantelle M; Patton, Richard L; Whiteley, Nia M; Driedzic, William R; McGaw, Iain J

    2016-01-01

    Osmoregulation and digestion are energetically demanding, and crabs that move into low salinity environments to feed must be able to balance the demands of both processes. Achieving this balance may pose greater challenges for weak than for efficient osmoregulators. This study examined the rate of oxygen consumption (MO2) of Carcinus maenas (efficient osmoregulator) and Cancer irroratus (weak osmoregulator) as a function of feeding and hyposaline stress. The MO2 increased 2-fold in both species following feeding. The MO2 increased and remained elevated in fasted crabs during acute hyposaline exposure. When hyposaline stress occurred after feeding, C. maenas responded with an immediate summation of the MO2 associated with feeding and hyposaline stress, whereas C. irroratus reacted with a partial summation of responses in a salinity of 24‰, but were unable to sum responses in 16‰. C. irroratus exhibited longer gut transit times. This may be due to an inability to regulate osmotic water onload as efficiently as C. maenas. Mechanical digestion in crabs can account for a significant portion of SDA, and a short term interruption led to the delay in summation of metabolic demands. Although protein synthesis is reported to account for the majority of SDA, this did not appear to be the case here. Protein synthesis rates were higher in C. irroratus but neither feeding or salinity affected protein synthesis rates of either species which suggests that protein synthesis can continue in low salinity as long as substrates are available. Copyright © 2015 Elsevier Inc. All rights reserved.

  17. Partial Support Ventilation and Mitochondrial-Targeted Antioxidants Protect against Ventilator-Induced Decreases in Diaphragm Muscle Protein Synthesis.

    PubMed

    Hudson, Matthew B; Smuder, Ashley J; Nelson, W Bradley; Wiggs, Michael P; Shimkus, Kevin L; Fluckey, James D; Szeto, Hazel H; Powers, Scott K

    2015-01-01

    Mechanical ventilation (MV) is a life-saving intervention in patients in respiratory failure. Unfortunately, prolonged MV results in the rapid development of diaphragm atrophy and weakness. MV-induced diaphragmatic weakness is significant because inspiratory muscle dysfunction is a risk factor for problematic weaning from MV. Therefore, developing a clinical intervention to prevent MV-induced diaphragm atrophy is important. In this regard, MV-induced diaphragmatic atrophy occurs due to both increased proteolysis and decreased protein synthesis. While efforts to impede MV-induced increased proteolysis in the diaphragm are well-documented, only one study has investigated methods of preserving diaphragmatic protein synthesis during prolonged MV. Therefore, we evaluated the efficacy of two therapeutic interventions that, conceptually, have the potential to sustain protein synthesis in the rat diaphragm during prolonged MV. Specifically, these experiments were designed to: 1) determine if partial-support MV will protect against the decrease in diaphragmatic protein synthesis that occurs during prolonged full-support MV; and 2) establish if treatment with a mitochondrial-targeted antioxidant will maintain diaphragm protein synthesis during full-support MV. Compared to spontaneously breathing animals, full support MV resulted in a significant decline in diaphragmatic protein synthesis during 12 hours of MV. In contrast, diaphragm protein synthesis rates were maintained during partial support MV at levels comparable to spontaneous breathing animals. Further, treatment of animals with a mitochondrial-targeted antioxidant prevented oxidative stress during full support MV and maintained diaphragm protein synthesis at the level of spontaneous breathing animals. We conclude that treatment with mitochondrial-targeted antioxidants or the use of partial-support MV are potential strategies to preserve diaphragm protein synthesis during prolonged MV.

  18. Lipase-catalyzed synthesis of partial acylglycerols of acetoacetate

    USDA-ARS?s Scientific Manuscript database

    A commercially available immobilized preparation of Rhizomucor miehei lipase (Lipozyme RMIM) has been employed in the synthesis of partial glycerides of acetoacetate. Due to the chemical reactivitity of the acetoacetyl group, these glycerides could have novel uses in e.g. polymer formation. Both 1...

  19. Large-scale and highly efficient synthesis of micro- and nano-fibers with controlled fiber morphology by centrifugal jet spinning for tissue regeneration

    NASA Astrophysics Data System (ADS)

    Ren, Liyun; Pandit, Vaibhav; Elkin, Joshua; Denman, Tyler; Cooper, James A.; Kotha, Shiva P.

    2013-02-01

    PLLA fibrous tissue scaffolds with controlled fiber nanoscale surface roughness are fabricated with a novel centrifugal jet spinning process. The centrifugal jet spinning technique is a highly efficient synthesis method for micron- to nano-sized fibers with a production rate up to 0.5 g min-1. During the centrifugal jet spinning process, a polymer solution jet is stretched by the centrifugal force of a rotating chamber. By engineering the rheological properties of the polymer solution, solvent evaporation rate and centrifugal force that are applied on the solution jet, polyvinylpyrrolidone (PVP) and poly(l-lactic acid) (PLLA) composite fibers with various diameters are fabricated. Viscosity measurements of polymer solutions allowed us to determine critical polymer chain entanglement limits that allow the generation of continuous fiber as opposed to beads or beaded fibers. Above a critical concentration at which polymer chains are partially or fully entangled, lower polymer concentrations and higher centrifugal forces resulted in thinner fibers. Etching of PVP from the PLLA-PVP composite fibers doped with increasing PVP concentrations yielded PLLA fibers with increasing nano-scale surface roughness and porosity, which increased the fiber hydrophilicity dramatically. Scanning electron micrographs of the etched composite fibers suggest that PVP and PLLA were co-contiguously phase separated within the composite fibers during spinning and nano-scale roughness features were created after the partial etching of PVP. To study the tissue regeneration efficacy of the engineered PLLA fiber matrix, human dermal fibroblasts are used to simulate partial skin graft. Fibers with increased PLLA surface roughness and porosity demonstrated a trend towards higher cell attachment and proliferation.PLLA fibrous tissue scaffolds with controlled fiber nanoscale surface roughness are fabricated with a novel centrifugal jet spinning process. The centrifugal jet spinning technique is a highly efficient synthesis method for micron- to nano-sized fibers with a production rate up to 0.5 g min-1. During the centrifugal jet spinning process, a polymer solution jet is stretched by the centrifugal force of a rotating chamber. By engineering the rheological properties of the polymer solution, solvent evaporation rate and centrifugal force that are applied on the solution jet, polyvinylpyrrolidone (PVP) and poly(l-lactic acid) (PLLA) composite fibers with various diameters are fabricated. Viscosity measurements of polymer solutions allowed us to determine critical polymer chain entanglement limits that allow the generation of continuous fiber as opposed to beads or beaded fibers. Above a critical concentration at which polymer chains are partially or fully entangled, lower polymer concentrations and higher centrifugal forces resulted in thinner fibers. Etching of PVP from the PLLA-PVP composite fibers doped with increasing PVP concentrations yielded PLLA fibers with increasing nano-scale surface roughness and porosity, which increased the fiber hydrophilicity dramatically. Scanning electron micrographs of the etched composite fibers suggest that PVP and PLLA were co-contiguously phase separated within the composite fibers during spinning and nano-scale roughness features were created after the partial etching of PVP. To study the tissue regeneration efficacy of the engineered PLLA fiber matrix, human dermal fibroblasts are used to simulate partial skin graft. Fibers with increased PLLA surface roughness and porosity demonstrated a trend towards higher cell attachment and proliferation. Electronic supplementary information (ESI) available. See DOI: 10.1039/c3nr33423f

  20. A COMPARISON OF EXPERIMENTS AND THREE-DIMENSIONAL ANALYSIS TECHNIQUES. PART II. UNPOISONED UNIFORM SLAB CORE WITH A PARTIALLY INSERTED HAFNIUM ROD AND A PARTIALLY INSERTED WATER GAP

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

    Roseberry, R.J.

    The experimental measurements and nuclear analysis of a uniformly loaded, unpoisoned slab core with a partially inserted hafnium rod and/or a partially inserted water gap are described. Comparisons of experimental data with calculated results of the UFO core and flux synthesis techniques are given. It is concluded that one of the flux synthesis techniques and the UFO code are able to predict flux distributions to within approximately -5% of experiment for most cases, with a maximum error of approximately -10% for a channel at the core- reflector boundary. The second synthesis technique failed to give comparable agreement with experiment evenmore » when various refinements were used, e.g. increasing the number of mesh points, performing the flux synthesis technique of iteration, and spectrum-weighting the appropriate calculated fluxes through the use of the SWAKRAUM code. These results are comparable to those reported in Part I of this study. (auth)« less

  1. SYNTHESIS OF PARTIAL-OXYGENATED HYDROCARBONS USING PHOTOCATALYSIS IN A LAMINAR FALLING FILM SLURRY REACTOR

    EPA Science Inventory

    The search for "Green" alternative processes for the oxidation of hydrocarbons selectively to partial oxygenates has been the subject of intense chemical research for many years. The USEPA is currently investigating an alternative synthesis pathway for the production of alcoho...

  2. SYNTHESIS OF PARTIALLY-OXYGENATED HYDROCARBONS USING PHOTOCATALYSIS IN A LAMINAR FALLING FILM SLURRY REACTOR

    EPA Science Inventory

    The search for "Green" alternative processes for the oxidation of hydrocarbons selectively to partial oxygenates has been the subject of intense chemical research for many years. The USEPA is currently investigating an alternative synthesis pathway for the production of alcoho...

  3. Engineering Yarrowia lipolytica as a platform for synthesis of drop-in transportation fuels and oleochemicals

    PubMed Central

    Xu, Peng; Qiao, Kangjian; Ahn, Woo Suk; Stephanopoulos, Gregory

    2016-01-01

    Harnessing lipogenic pathways and rewiring acyl-CoA and acyl-ACP (acyl carrier protein) metabolism in Yarrowia lipolytica hold great potential for cost-efficient production of diesel, gasoline-like fuels, and oleochemicals. Here we assessed various pathway engineering strategies in Y. lipolytica toward developing a yeast biorefinery platform for sustainable production of fuel-like molecules and oleochemicals. Specifically, acyl-CoA/acyl-ACP processing enzymes were targeted to the cytoplasm, peroxisome, or endoplasmic reticulum to generate fatty acid ethyl esters and fatty alkanes with tailored chain length. Activation of endogenous free fatty acids and the subsequent reduction of fatty acyl-CoAs enabled the efficient synthesis of fatty alcohols. Engineering a hybrid fatty acid synthase shifted the free fatty acids to a medium chain-length scale. Manipulation of alternative cytosolic acetyl-CoA pathways partially decoupled lipogenesis from nitrogen starvation and unleashed the lipogenic potential of Y. lipolytica. Taken together, the strategies reported here represent promising steps to develop a yeast biorefinery platform that potentially upgrades low-value carbons to high-value fuels and oleochemicals in a sustainable and environmentally friendly manner. PMID:27621436

  4. Age-dependent epigenetic control of differentiation inhibitors is critical for remyelination efficiency

    PubMed Central

    Shen, Siming; Sandoval, Juan; Swiss, Victoria A; Li, Jiadong; Dupree, Jeff; Franklin, Robin J M; Casaccia-Bonnefil, Patrizia

    2009-01-01

    The efficiency of remyelination decreases with age, but the molecular mechanisms responsible for this decline remain only partially understood. In this study, we show that remyelination is regulated by age-dependent epigenetic control of gene expression. In demyelinated young brains, new myelin synthesis is preceded by downregulation of oligodendrocyte differentiation inhibitors and neural stem cell markers, and this is associated with recruitment of histone deacetylases (HDACs) to promoter regions. In demyelinated old brains, HDAC recruitment is inefficient, and this allows the accumulation of transcriptional inhibitors and prevents the subsequent surge in myelin gene expression. Defective remyelination can be recapitulated in vivo in mice receiving systemic administration of pharmacological HDAC inhibitors during cuprizone treatment and is consistent with in vitro results showing defective differentiation of oligodendrocyte progenitors after silencing specific HDAC isoforms. Thus, we suggest that inefficient epigenetic modulation of the oligodendrocyte differentiation program contributes to the age-dependent decline in remyelination efficiency. PMID:19160500

  5. Synthesis of Bisindole Alkaloids from the Apocynaceae Which Contain a Macroline or Sarpagine Unit: A Review

    PubMed Central

    Rahman, Md Toufiqur; Phani Babu Tiruveedhula, Veera V. N.; Cook, James M.

    2016-01-01

    Bisindole natural products consist of two monomeric indole alkaloid units as their obligate constituents. Bisindoles are more potent with respect to their biological activity than their corresponding monomeric units. In addition, the synthesis of bisindoles are far more challenging than the synthesis of monomeric indole alkaloids. Herein is reviewed the enantiospecific total and partial synthesis of bisindole alkaloids isolated primarily from the Alstonia genus of the Apocynaceae family. The monomeric units belong to the sarpagine, ajmaline, macroline, vobasine, and pleiocarpamine series. An up-to-date discussion of their isolation, characterization, biological activity as well as approaches to their partial and total synthesis by means of both synthetic and biosynthetic strategies are presented. PMID:27854259

  6. Fully Converting Graphite into Graphene Oxide Hydrogels by Preoxidation with Impure Manganese Dioxide.

    PubMed

    Sun, Jiaojiao; Yang, Ningxin; Sun, Zhe; Zeng, Mengqi; Fu, Lei; Hu, Chengguo; Hu, Shengshui

    2015-09-30

    Potassium permanganate (KMnO4) has been proved to be an efficient oxidant for converting graphite into graphite oxide, but its slow diffusion in the interlayer of graphite seriously restricts the production of graphene oxide (GO). Here, we demonstrate that the preoxidation of graphite by impure manganese dioxide (MnO2) in a mixture of concentrated sulfuric acid (H2SO4) and phosphorus pentoxide (P2O5) can efficiently improve the synthesis of GO when KMnO4 is employed as the oxidant. The prepared honey-like GO hydrogels possess a high yield of single-layer sheets, large sizes (average lateral size up to 20 μm), wide ranges of stable dispersion concentrations (from dilute solutions, viscous hydrogels, to dry films), and good conductivity after reduction (~2.9 × 10(4) S/m). The mechanism for the improved synthesis of GO by impure MnO2 was explored. The enhanced exfoliation and oxidation of graphite by oxidative Mn ions (mainly Mn(3+)), which are synergistically produced by the reaction of impure MnO2 with H2SO4 and P2O5, are found to be responsible for the improved synthesis of such GO hydrogels. Particularly, preoxidized graphite (POG) can be partially dispersed in water with sonication, which allows the facile construction of flexible and highly conductive graphene nanosheet film electrodes with excellent electrochemical sensing properties.

  7. A COMPARISON OF EXPERIMENTS AND THREE-DIMENSIONAL ANALYSIS TECHNIQUES. PART I. UNPOISONED UNIFORM SLAB CORE WITH A PARTIALLY INSERTED HAFNIUM ROD

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

    Renzi, N.E.; Roseberry, R.J.

    >The experimental measurements and nuclear analysis of a uniformly loaded, unpoisoned slab core with a partially insented hafnium rod are described. Comparisons of experimental data with calculated results of the UFO code and flux synthesis techniques are given. It was concluded that one of the flux synthesis techniques and the UFO code are able to predict flux distributions to within approximately 5% of experiment for most cases. An error of approximately 10% was found in the synthesis technique for a channel near the partially inserted rod. The various calculations were able to predict neutron pulsed shutdowns to only approximately 30%.more » (auth)« less

  8. Novel alkyd-type coating resins produced using cationic polymerization

    DOE PAGES

    Chisholm, Bret J.; Kalita, Harjyoti; Alam, Samim; ...

    2015-05-06

    Novel, partially bio-based poly(vinyl ether) copolymers derived from soybean oil and cyclohexyl vinyl ether (CHVE) were produced by cationic polymerization and investigated for application as alkyd-type surface coatings. Compared to conventional alkyd resins, which are produced by high temperature melt condensation polymerization, the poly(v9nyl ether)s provide several advantages. These advantages include milder, more energy efficient polymer synthesis, elimination of issues associated with gelation during polymer synthesis, production of polymers with well-defined composition and relatively narrow molecular weight distribution, and elimination of film formation and physical property issues associated with entrained monomers, dimers, trimers, etc. The results of the studied showedmore » that the thermal, mechanical, and physical properties of the coatings produced from these novel polymers varied considerably as a function of polymer composition and cure temperature. Overall, the results suggest a good potential for these novel copolymers to be used for coatings cured by autoxidation.« less

  9. In vitro studies on the translocation of acid phosphatase into the endoplasmic reticulum of the yeast Saccharomyces cerevisiae.

    PubMed

    Krebs, H O; Hoffschulte, H K; Müller, M

    1989-05-01

    We demonstrate here the in vitro translocation of yeast acid phosphatase into rough endoplasmic reticulum. The precursor of the repressible acid phosphatase from Saccharomyces cerevisiae encoded by the PHO5 gene, was synthesized in a yeast lysate programmed with in vitro transcribed PHO5 mRNA. In the presence of yeast rough microsomes up to 16% of the acid phosphatase synthesized was found to be translocated into the microsomes, as judged by proteinase resistance, and fully core-glycosylated. The translocation efficiency however, decreased to 3% if yeast rough microsomes were added after synthesis of acid phosphatase had been terminated. When a wheat-germ extract was used for in vitro synthesis, the precursor of acid phosphatase was translocated into canine pancreatic rough microsomes and thereby core-glycosylated in a signal-recognition-particle-dependent manner. Replacing canine with yeast rough microsomes in the wheat-germ translation system, however, resulted in a significant decrease in the ability to translocate and glycosylate the precursor. Translocation and glycosylation were partially restored by a high-salt extract prepared from yeast ribosomes. The results presented here suggest that yeast-specific factors are needed to translocate and glycosylate acid phosphatase efficiently in vitro.

  10. Regulation of insulin preRNA splicing by glucose

    PubMed Central

    Wang, Juehu; Shen, Luping; Najafi, Habiba; Kolberg, Janice; Matschinsky, Franz M.; Urdea, Mickey; German, Michael

    1997-01-01

    Glucose tightly regulates the synthesis and secretion of insulin by β cells in the pancreatic islets of Langerhans. To investigate whether glucose regulates insulin synthesis at the level of insulin RNA splicing, we developed a method to detect and quantify a small amount of RNA by using the branched DNA (bDNA) signal-amplification technique. This assay is both sensitive and highly specific: mouse insulin II mRNA can be detected from a single β cell (βTC3 cells or mouse islets), whereas 1 million non-insulin-producing α cells (αTC1.6 cells) give no signal. By using intron and exon sequences, oligonucleotide probes were designed to distinguish the various unspliced and partially spliced insulin preRNAs from mature insulin mRNA. Insulin RNA splicing rates were estimated from the rate of disappearance of insulin preRNA signal from β cells treated with actinomycin D to block transcription. We found that the two introns in mouse insulin II are not spliced with the same efficiency. Intron 2 is spliced out more efficiently than intron 1. As a result, some mRNA retaining intron 1 enters the cytoplasm, making up ≈2-10% of insulin mRNA in the cell. This partially spliced cytoplasmic mRNA is quite stable, with a half-life similar to the completely spliced form. When islets grown in high glucose are shifted to low glucose medium, the level of insulin preRNA and the rate of splicing fall significantly. We conclude that glucose stimulates insulin gene transcription and insulin preRNA splicing. Previous estimates of insulin transcription rates based on insulin preRNA levels that did not consider the rate of splicing may have underestimated the effect of glucose on insulin gene transcription. PMID:9113994

  11. Compartmental modeling with nitrogen-15 to determine effects of degree of fat saturation on intraruminal N recycling.

    PubMed

    Oldick, B S; Firkins, J L; Kohn, R A

    2000-09-01

    Two- and three-compartment models were developed to describe N kinetics within the rumen using three Holstein heifers and one nonlactating Holstein cow fitted with ruminal and duodenal cannulas. A 4 x 4 Latin square design included a control diet containing no supplemental fat and diets containing 4.85% of diet dry matter as partially hydrogenated tallow (iodine value = 13), tallow (iodine value = 51), or animal-vegetable fat (iodine value = 110). Effects of fat on intraruminal N recycling and relationships between intraruminal N recycling and ruminal protozoa concentration or the efficiency of microbial protein synthesis were determined. A pulse dose of 15(NH4)2SO4 was introduced into the ruminal NH3 N pool, and samples were taken over time from the ruminal NH3 N and nonammonia N pools. For the three-compartment model, precipitates of nonammonia N after trichloroacetic acid and ethanol extraction were defined as slowly turning over nonammonia N; rapidly turning over nonammonia N was determined by difference. Curves of 15N enrichment were fit to models with two (NH3 N and nonammonia N) or three (NH3 N, rapidly turning over nonammonia N, and slowly turning over nonammonia N) compartments using the software SAAM II. Because the three-compartment model did not remove a small systematic bias or improve the fit of the data, the two-compartment model was used to provide measurements of intraruminal N recycling. Intraruminal NH3 N recycling (45% for control) decreased linearly as fat unsaturation increased (50.2, 43.0, and 41.7% for partially hydrogenated tallow, tallow, and animal-vegetable fat, respectively). Intraruminal nitrogen recycling was not correlated with efficiency of microbial protein synthesis or ruminal protozoa counts.

  12. Highly efficient enzymatic synthesis of tert-butyl (S)-6-chloro-5-hydroxy-3-oxohexanoate with a mutant alcohol dehydrogenase of Lactobacillus kefir.

    PubMed

    He, Xiu-Juan; Chen, Shao-Yun; Wu, Jian-Ping; Yang, Li-Rong; Xu, Gang

    2015-11-01

    tert-Butyl (S)-6-chloro-5-hydroxy-3-oxohexanoate ((S)-CHOH) is a valuable chiral synthon, which is used for the synthesis of the cholesterol-lowering drugs atorvastatin and rosuvastatin. To date, only the alcohol dehydrogenases from Lactobacillus brevis (LbADH) and Lactobacillus kefir (LkADH) have demonstrated catalytic activity toward the asymmetric reduction of tert-butyl 6-chloro-3,5-dioxohexanoate (CDOH) to (S)-CHOH. Herein, a tetrad mutant of LkADH (LkTADH), A94T/F147L/L199H/A202L, was screened to be more efficient in this bioreduction process, exhibiting a 3.7- and 42-fold improvement in specific activity toward CDOH (1.27 U/mg) over LbADH (0.34 U/mg) and wild-type LkADH (0.03 U/mg), respectively. The molecular basis for the improved catalytic activity of LkTADH toward CDOH was investigated using homology modeling and docking analysis. Two major issues had a significant impact on the biocatalytic efficiency of this process, including (i) the poor aqueous stability of the substrate and (ii) partial substrate inhibition. A fed-batch strategy was successfully developed to address these issues and maintain a suitably low substrate concentration throughout the entire process. Several other parameters were also optimized, including the pH, temperature, NADP(+) concentration and cell loading. A final CDOH concentration of 427 mM (100 g/L) gave (S)-CHOH in 94 % yield and 99.5 % e.e. after a reaction time of 38 h with whole cells expressing LkTADH. The space-time yield and turnover number of NADP(+) in this process were 10.6 mmol/L/h and 16,060 mol/mol, respectively, which were the highest values ever reported. This new approach therefore represents a promising alternative for the efficient synthesis of (S)-CHOH.

  13. The chemical energy unit partial oxidation reactor operation simulation modeling

    NASA Astrophysics Data System (ADS)

    Mrakin, A. N.; Selivanov, A. A.; Batrakov, P. A.; Sotnikov, D. G.

    2018-01-01

    The chemical energy unit scheme for synthesis gas, electric and heat energy production which is possible to be used both for the chemical industry on-site facilities and under field conditions is represented in the paper. The partial oxidation reactor gasification process mathematical model is described and reaction products composition and temperature determining algorithm flow diagram is shown. The developed software product verification showed good convergence of the experimental values and calculations according to the other programmes: the temperature determining relative discrepancy amounted from 4 to 5 %, while the absolute composition discrepancy ranged from 1 to 3%. The synthesis gas composition was found out practically not to depend on the supplied into the partial oxidation reactor (POR) water vapour enthalpy and compressor air pressure increase ratio. Moreover, air consumption coefficient α increase from 0.7 to 0.9 was found out to decrease synthesis gas target components (carbon and hydrogen oxides) specific yield by nearly 2 times and synthesis gas target components required ratio was revealed to be seen in the water vapour specific consumption area (from 5 to 6 kg/kg of fuel).

  14. Synthesis gas and olefins from the catalytic autothermal reforming of volatile and non-volatile liquids

    NASA Astrophysics Data System (ADS)

    Dreyer, Bradon Justin

    2007-12-01

    The research presented in this thesis develops an understanding of a clean energy process technology, catalytic partial oxidation (CPO). CPO is a process in which a carbon containing fuel, such as a hydrocarbon, is passed over a noble metal catalyst (e.g. rhodium and platinum) to efficiently generate synthesis gas (H2 and CO) and olefins (e.g. ethylene and propylene) in millisecond contact times. Chapter 1 introduces CPO and compares this technology with conventional methods for synthesis gas and olefin production. CPO has several advantages over the traditional synthesis gas and olefin production methods. One advantage includes autothermal operation, requiring no external heat input from furnaces or heat exchangers. Autothermal operation allows these reactors to be built compactly. The short contact-times associated with CPO further enable for high throughput in relatively small reactor systems, and more compact reactors typically translate to faster response times if transient operation is required. Nobel metal based CPO catalysts are also resistant to deactivation, resulting in less catalyst replacement, regeneration, and maintenance, and an increase in operating efficiency. An overview of the many applications of the chemicals produced from CPO is also presented in Chapter 1. The chemicals produced are crucial in generating valuable chemical intermediates that are eventually incorporated in consumer products, medical devices, building structures, and fertilizers. Additionally, H2 can be used as a source of energy in mobile fuel applications. Fuel cells convert H2 and O2 into electricity and water at higher efficiencies than thermal engine generators. Due to the difficulties in H2 storage, these more efficient energy generators are dependent on hydrogen obtained from synthesis gas production in compact, portable fuel reformers, such as CPO reactors. Furthermore, H2 and CO can be used in reducing environmentally harmful emissions. Particularly, the implementation of NOx traps and hydrogen into diesel engines has shown potential in reducing NOx emissions into the environment. Both concepts are dependent on synthesis gas generated from portable, compact fuel reformers, such as CPO reactors. Chapter 1 also reviews previous research in CPO, along with several important experimental parameters, and outlines the remaining research directions in the remaining chapters. In Chapter 2, steam addition to the CPO of higher hydrocarbons was explored over rhodium-coated ceramic foam supports at millisecond contact times. Steam addition to the CPO of n-decane and n-hexadecane in air produced considerably higher H2 and CO2 and lower olefin and CO selectivities than traditional CPO. For steam to carbon feed ratios from 0.0 to 4.0, the reactor operated autothermally, and the H2 to CO product ratio increased from ˜1.0 to ˜4.0, which is essentially the equilibrium product composition near synthesis gas stoichiometry (C/O ˜1) at contact times of ˜7 milliseconds. In fuel-rich feeds exceeding the synthesis gas ratio (C/O > 1), steam addition suppressed olefins, promoted synthesis gas and water-gas shift products, and reduced catalyst surface carbon. Furthermore, steam addition to the CPO of the military fuel JP-8 was performed successfully, also increasing H2 and suppressing olefins. (Abstract shortened by UMI.)

  15. A defect in homologous recombination leads to increased translesion synthesis in E. coli

    PubMed Central

    Naiman, Karel; Pagès, Vincent; Fuchs, Robert P.

    2016-01-01

    DNA damage tolerance pathways allow cells to duplicate their genomes despite the presence of replication blocking lesions. Cells possess two major tolerance strategies, namely translesion synthesis (TLS) and homology directed gap repair (HDGR). TLS pathways involve specialized DNA polymerases that are able to synthesize past DNA lesions with an intrinsic risk of causing point mutations. In contrast, HDGR pathways are essentially error-free as they rely on the recovery of missing information from the sister chromatid by RecA-mediated homologous recombination. We have investigated the genetic control of pathway choice between TLS and HDGR in vivo in Escherichia coli. In a strain with wild type RecA activity, the extent of TLS across replication blocking lesions is generally low while HDGR is used extensively. Interestingly, recA alleles that are partially impaired in D-loop formation confer a decrease in HDGR and a concomitant increase in TLS. Thus, partial defect of RecA's capacity to invade the homologous sister chromatid increases the lifetime of the ssDNA.RecA filament, i.e. the ‘SOS signal’. This increase favors TLS by increasing both the TLS polymerase concentration and the lifetime of the TLS substrate, before it becomes sequestered by homologous recombination. In conclusion, the pathway choice between error-prone TLS and error-free HDGR is controlled by the efficiency of homologous recombination. PMID:27257075

  16. Single-atom Catalysis Using Pt/Graphene Achieved through Atomic Layer Deposition

    NASA Astrophysics Data System (ADS)

    Sun, Shuhui; Zhang, Gaixia; Gauquelin, Nicolas; Chen, Ning; Zhou, Jigang; Yang, Songlan; Chen, Weifeng; Meng, Xiangbo; Geng, Dongsheng; Banis, Mohammad N.; Li, Ruying; Ye, Siyu; Knights, Shanna; Botton, Gianluigi A.; Sham, Tsun-Kong; Sun, Xueliang

    2013-05-01

    Platinum-nanoparticle-based catalysts are widely used in many important chemical processes and automobile industries. Downsizing catalyst nanoparticles to single atoms is highly desirable to maximize their use efficiency, however, very challenging. Here we report a practical synthesis for isolated single Pt atoms anchored to graphene nanosheet using the atomic layer deposition (ALD) technique. ALD offers the capability of precise control of catalyst size span from single atom, subnanometer cluster to nanoparticle. The single-atom catalysts exhibit significantly improved catalytic activity (up to 10 times) over that of the state-of-the-art commercial Pt/C catalyst. X-ray absorption fine structure (XAFS) analyses reveal that the low-coordination and partially unoccupied densities of states of 5d orbital of Pt atoms are responsible for the excellent performance. This work is anticipated to form the basis for the exploration of a next generation of highly efficient single-atom catalysts for various applications.

  17. GaN for LED applications

    NASA Technical Reports Server (NTRS)

    Pankove, J. I.

    1973-01-01

    In order to improve the synthesis of GaN the effect of various growth and doping parameters has been studied. Although Be, Li, Mg, and Dy can be used to overcompensate native donors, the most interesting acceptor element is Zn. The emission spectrum and the luminescence efficiency depend on the growth temperature (below 800 C), on the partial pressure of the doping impurity, and on the duration of growth. Blue-green electroluminescence with a power efficiency of 0.1 percent and a brightness of 850 fL (at 0.6 mA and 22.5 V) was obtained. Some diodes allow the color of the emitted light to change by reversing the polarity of the bias. Continuous operation of a diode over a period of 5 months showed no evidence of degradation. The luminescence properties of ion-implanted GaN were studied. Delay effects were found in the electroluminescence of diodes, although, with a dc bias, a 70-MHz modulation was possible.

  18. Single-atom Catalysis Using Pt/Graphene Achieved through Atomic Layer Deposition

    PubMed Central

    Sun, Shuhui; Zhang, Gaixia; Gauquelin, Nicolas; Chen, Ning; Zhou, Jigang; Yang, Songlan; Chen, Weifeng; Meng, Xiangbo; Geng, Dongsheng; Banis, Mohammad N.; Li, Ruying; Ye, Siyu; Knights, Shanna; Botton, Gianluigi A.; Sham, Tsun-Kong; Sun, Xueliang

    2013-01-01

    Platinum-nanoparticle-based catalysts are widely used in many important chemical processes and automobile industries. Downsizing catalyst nanoparticles to single atoms is highly desirable to maximize their use efficiency, however, very challenging. Here we report a practical synthesis for isolated single Pt atoms anchored to graphene nanosheet using the atomic layer deposition (ALD) technique. ALD offers the capability of precise control of catalyst size span from single atom, subnanometer cluster to nanoparticle. The single-atom catalysts exhibit significantly improved catalytic activity (up to 10 times) over that of the state-of-the-art commercial Pt/C catalyst. X-ray absorption fine structure (XAFS) analyses reveal that the low-coordination and partially unoccupied densities of states of 5d orbital of Pt atoms are responsible for the excellent performance. This work is anticipated to form the basis for the exploration of a next generation of highly efficient single-atom catalysts for various applications.

  19. Homogeneous synthesis of Ag nanoparticles-doped water-soluble cellulose acetate for versatile applications.

    PubMed

    Cao, Jie; Sun, Xunwen; Zhang, Xinxing; Lu, Canhui

    2016-11-01

    We report a facile and efficient approach for synthesis of well-dispersed and stable silver nanoparticles (Ag NPs) using water-soluble cellulose acetate (CA) as both reductant and stabilizer. Partially substituted CA with highly active hydroxyl groups and excellent water-solubility is able to reduce silver ions in homogeneous aqueous medium effectively. The synthesized Ag NPs were characterized by UV-vis spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy and energy dispersive X-ray spectroscope analysis. The as-prepared Ag NPs were well-dispersed, showing a surface plasmon resonance peak at 426nm. The resulted Ag NPs@CA nanohybrids exhibit high catalytic activity for the reduction of 4-nitrophenol to 4-aminophenol in the presence of NaBH 4 . Meanwhile, the nanohybrids are also effective in inhibiting the growth of bacterial. This environmentally friendly method promotes the use of renewable natural resources to prepare a variety of inorganic-organic materials for catalysis, antibacterial, sensors and other applications. Copyright © 2016 Elsevier B.V. All rights reserved.

  20. Kynurenine Pathway Metabolism is Involved in the Maintenance of the Intracellular NAD+ Concentration in Human Primary Astrocytes

    PubMed Central

    Grant, Ross; Nguyen, Susan; Guillemin, Gilles

    2010-01-01

    Efficient synthesis of NAD+ is critical to maintaining cell viability in all organs of the body. However, little is known of the pathway(s) by which cells of the central nervous system produce NAD+. The aim of this study was to investigate the relationship, between tryptophan degradation via the kynurenine pathway (KP) and de novo NAD+ synthesis in human astrocytes, a major cell type within the brain. In this study we observed that inhibition of single enzymes of the KP resulted in significant decreases in NAD+ levels in astroglial cells after a 24 hr period. We also observed that astrocytes cultured in media deficient in tryptophan, nicotinic acid and nicotinamide resulted in a 50% decrease in NAD+ levels after 24 hrs. This decrease in NAD+ was partially restored by supplementation of the culture media with either tryptophan or kynurenine, or nicotinic acid or with supply of the salvage pathway precursor nicotinamide. PMID:22084595

  1. Silencing of the pentose phosphate pathway genes influences DNA replication in human fibroblasts.

    PubMed

    Fornalewicz, Karolina; Wieczorek, Aneta; Węgrzyn, Grzegorz; Łyżeń, Robert

    2017-11-30

    Previous reports and our recently published data indicated that some enzymes of glycolysis and the tricarboxylic acid cycle can affect the genome replication process by changing either the efficiency or timing of DNA synthesis in human normal cells. Both these pathways are connected with the pentose phosphate pathway (PPP pathway). The PPP pathway supports cell growth by generating energy and precursors for nucleotides and amino acids. Therefore, we asked if silencing of genes coding for enzymes involved in the pentose phosphate pathway may also affect the control of DNA replication in human fibroblasts. Particular genes coding for PPP pathway enzymes were partially silenced with specific siRNAs. Such cells remained viable. We found that silencing of the H6PD, PRPS1, RPE genes caused less efficient enterance to the S phase and decrease in efficiency of DNA synthesis. On the other hand, in cells treated with siRNA against G6PD, RBKS and TALDO genes, the fraction of cells entering the S phase was increased. However, only in the case of G6PD and TALDO, the ratio of BrdU incorporation to DNA was significantly changed. The presented results together with our previously published studies illustrate the complexity of the influence of genes coding for central carbon metabolism on the control of DNA replication in human fibroblasts, and indicate which of them are especially important in this process. Copyright © 2017 Elsevier B.V. All rights reserved.

  2. Process for production desulfurized of synthesis gas

    DOEpatents

    Wolfenbarger, James K.; Najjar, Mitri S.

    1993-01-01

    A process for the partial oxidation of a sulfur- and silicate-containing carbonaceous fuel to produce a synthesis gas with reduced sulfur content which comprises partially oxidizing said fuel at a temperature in the range of 1900.degree.-2600.degree. F. in the presence of a temperature moderator, an oxygen-containing gas and a sulfur capture additive which comprises a calcium-containing compound portion, a sodium-containing compound portion, and a fluoride-containing compound portion to produce a synthesis gas comprising H.sub.2 and CO with a reduced sulfur content and a molten slag which comprises (1) a sulfur-containing sodium-calcium-fluoride silicate phase; and (2) a sodium-calcium sulfide phase.

  3. Elucidation of Two Giants: Challenges to Thick-shell Synthesis in CdSe/ZnSe and ZnSe/CdS Core/Shell Quantum Dots

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

    Acharya, Krishna P.; Nguyen, Hue M.; Paulite, Melissa

    2015-03-06

    Core/thick-shell "giant" quantum dots (gQDs) possessing type II electronic structures exhibit suppressed blinking and diminished nonradiative Auger recombination. Here we investigate CdSe/ZnSe and ZnSe/CdS as potential new gQDs. We show theoretically and experimentally that both can exhibit partial or complete spatial separation of an excited-state electron–hole pair (i.e., type II behavior). However, we reveal that thick-shell growth is challenged by competing processes: alloying and cation exchange. We demonstrate that these can be largely avoided by choice of shelling conditions (e.g., time, temperature, and QD core identity). The resulting CdSe/ZnSe gQDs exhibit unusual single-QD properties, principally emitting from dim gray statesmore » but having high two-exciton (biexciton) emission efficiencies, whereas ZnSe/CdS gQDs show characteristic gQD blinking suppression, though only if shelling is accompanied by partial cation exchange.« less

  4. An Efficient Synthesis of Dicycloalkylacetylenes: 1,2-Dicyclopropylethyne and (cyclopropylethynyl)cyclobutane (Preprint)

    DTIC Science & Technology

    2008-11-05

    ANSI Std. 239.18 The Distribution A : “Approved for public release; distribution unlimited.” An Efficient Synthesis of Dicycloalkylacetylenes: 1 ... synthesis of terminal/internal alkynes involve the alkynylation of alkylhalide with metal acetylide 1 or base promoted dehydrohalogenation 2 of...chloropent- 1 -yne (5, 57%) 9 and 1,8- dichlorooct- 1 -yne(9, 36%). 8 We report here an efficient and economical synthesis of dicycloalkylethynes namely

  5. Exchanging partially hydrogenated fat for palmitic acid in the diet increases LDL-cholesterol and endogenous cholesterol synthesis in normocholesterolemic women.

    PubMed

    Sundram, Kalyana; French, Margaret A; Clandinin, M Thomas

    2003-08-01

    Partial hydrogenation of oil results in fats containing unusual isomeric fatty acids characterized by cis and trans configurations. Hydrogenated fats containing trans fatty acids increase plasma total cholesterol (TC) and LDL-cholesterol while depressing HDL-cholesterol levels. Identifying the content of trans fatty acids by food labeling is overshadowed by a reluctance of health authorities to label saturates and trans fatty acids separately. Thus, it is pertinent to compare the effects of trans to saturated fatty acids using stable isotope methodology to establish if the mechanism of increase in TC and LDL-cholesterol is due to the increase in the rate of endogenous synthesis of cholesterol. Ten healthy normocholesterolemic female subjects consumed each of two diets containing approximately 30% of energy as fat for a fourweek period. One diet was high in palmitic acid (10.6% of energy) from palm olein and the other diet exchanged 5.6% of energy as partially hydrogenated fat for palmitic acid. This fat blend resulted in monounsaturated fatty acids decreasing by 4.9 % and polyunsaturated fats increasing by 2.7%. The hydrogenated fat diet treatment provided 3.1% of energy as elaidic acid. For each dietary treatment, the fractional synthesis rates for cholesterol were measured using deuterium-labeling procedures and blood samples were obtained for blood lipid and lipoprotein measurements. Subjects exhibited a higher total cholesterol and LDL-cholesterol level when consuming the diet containing trans fatty acids while also depressing the HDL-cholesterol level. Consuming the partially hydrogenated fat diet treatment increased the fractional synthesis rate of free cholesterol. Consumption of hydrogenated fats containing trans fatty acids in comparison to a mixtur e of palmitic and oleic acids increase plasma cholesterol levels apparently by increasing endogenous synthesis of cholesterol.

  6. Role of protein synthesis and DNA methylation in the consolidation and maintenance of long-term memory in Aplysia

    PubMed Central

    Pearce, Kaycey; Cai, Diancai; Roberts, Adam C; Glanzman, David L

    2017-01-01

    Previously, we reported that long-term memory (LTM) in Aplysia can be reinstated by truncated (partial) training following its disruption by reconsolidation blockade and inhibition of PKM (Chen et al., 2014). Here, we report that LTM can be induced by partial training after disruption of original consolidation by protein synthesis inhibition (PSI) begun shortly after training. But when PSI occurs during training, partial training cannot subsequently establish LTM. Furthermore, we find that inhibition of DNA methyltransferase (DNMT), whether during training or shortly afterwards, blocks consolidation of LTM and prevents its subsequent induction by truncated training; moreover, later inhibition of DNMT eliminates consolidated LTM. Thus, the consolidation of LTM depends on two functionally distinct phases of protein synthesis: an early phase that appears to prime LTM; and a later phase whose successful completion is necessary for the normal expression of LTM. Both the consolidation and maintenance of LTM depend on DNA methylation. DOI: http://dx.doi.org/10.7554/eLife.18299.001 PMID:28067617

  7. 7alpha- and 12alpha-Hydroxysteroid dehydrogenases from Acinetobacter calcoaceticus lwoffii: a new integrated chemo-enzymatic route to ursodeoxycholic acid.

    PubMed

    Giovannini, Pier Paolo; Grandini, Alessandro; Perrone, Daniela; Pedrini, Paola; Fantin, Giancarlo; Fogagnolo, Marco

    2008-12-22

    We report the very efficient biotransformation of cholic acid to 7-keto- and 7,12-diketocholic acids with Acinetobacter calcoaceticus lwoffii. The enzymes responsible of the biotransformation (i.e. 7alpha- and 12alpha-hydroxysteroid dehydrogenases) are partially purified and employed in a new chemo-enzymatic synthesis of ursodeoxycholic acid starting from cholic acid. The first step is the 12alpha-HSDH-mediated total oxidation of sodium cholate followed by the Wolf-Kishner reduction of the carbonyl group to chenodeoxycholic acid. This acid is then quantitatively oxidized with 7alpha-HSDH to 7-ketochenodeoxycholic acid, that was chemically reduced to ursodeoxycholic acid (70% overall yield).

  8. Synthesis of single-site copper catalysts for methane partial oxidation

    DOE PAGES

    Grundner, S.; Luo, W.; Sanchez-Sanchez, M.; ...

    2015-12-24

    Cu-Exchanged zeolites are known as active materials for methane oxidation to methanol. However, understanding of the formation of Cu active species during synthesis, dehydration and activation is fragmented and rudimentary. We show here how a synthesis protocol guided by insight in the ion exchange elementary steps leads to highly uniform Cu species in mordenite (MOR).

  9. Process for production of synthesis gas with reduced sulfur content

    DOEpatents

    Najjar, Mitri S.; Corbeels, Roger J.; Kokturk, Uygur

    1989-01-01

    A process for the partial oxidation of a sulfur- and silicate-containing carbonaceous fuel to produce a synthesis gas with reduced sulfur content which comprises partially oxidizing said fuel at a temperature in the range of 1800.degree.-2200.degree. F. in the presence of a temperature moderator, an oxygen-containing gas and a sulfur capture additive which comprises an iron-containing compound portion and a sodium-containing compound portion to produce a synthesis gas comprising H.sub.2 and CO with a reduced sulfur content and a molten slag which comprises (i) a sulfur-containing sodium-iron silicate phase and (ii) a sodium-iron sulfide phase. The sulfur capture additive may optionally comprise a copper-containing compound portion.

  10. Hierarchical Bayesian inference on genetic and non-genetic components of partial efficiencies determining feed efficiency in dairy cattle

    USDA-ARS?s Scientific Manuscript database

    Dairy cattle feed efficiency (FE) can be defined as the ability to convert DMI into milk energy (MILKE) and maintenance or metabolic body weight (MBW). In other words, DMI is conditional on MILKE and MBW (DMI|MILKE,MBW). These partial regressions or partial efficiencies (PE) of DMI on MILKE and MBW ...

  11. Genome-Edited, TH-expressing Neuroblastoma Cells as a Disease Model for Dopamine-Related Disorders: A Proof-of-Concept Study on DJ-1-deficient Parkinsonism

    PubMed Central

    Prasuhn, Jannik; Mårtensson, Christoph U.; Krajka, Victor; Klein, Christine; Rakovic, Aleksandar

    2018-01-01

    Impairment of the dopaminergic (DA) system is a common cause of several movement disorders including Parkinson’s disease (PD), however, little is known about the underlying disease mechanisms. The recent development of stem-cell-based protocols for the generation of DA neurons partially solved this issue, however, this technology is costly and time-consuming. Commonly used cell lines, i.e., neuroblastoma (SHSY5Y) and PC12 cells are still widely used to investigate PD and significantly contributed to our understanding of mechanisms involved in development of the disease. However, they either do not express DA at all or require additional, only partially efficient differentiations in order to produce DA. Here we generated and characterized transgenic SH-SY5Y cells, ectopically expressing tyrosine hydroxylase (SHTH+), that can be used as a homogenous, DA-producing model to study alterations in DA metabolism and oxidative stress. We demonstrated that SHTH+ produce high levels of DA, 3,4-dihydroxyphenylacetic acid (DOPAC), and homovanillic acid (HVA) making this model suitable to investigate not only alterations in DA synthesis but also its turnover. We also provide evidence for the presence of other enzymes involved in DA synthesis and its turnover in these cells. Finally, we showed that these cells can easily be genetically modified using CRISPR/Cas9 technology in order to study genetically defined forms of movement disorders using DJ1-linked PD as a model. PMID:29379417

  12. RNA turnover and protein synthesis in fish cells.

    PubMed

    Smith, R W; Palmer, R M; Houlihan, D F

    2000-03-01

    Protein synthesis in fish has been previously correlated with RNA content. The present study investigates whether protein and RNA synthesis rates are similarly related. Protein and RNA synthesis rates were determined from 3H-phenylalanine and 3H-uridine incorporation, respectively, and expressed as % x day(-1) and half-lives, respectively. Three fibroblast cell lines were used: BF-2, RTP, CHSE 214, which are derived from the bluegill, rainbow trout and Chinook salmon, respectively. These cells contained similar RNA concentrations (approximately 175 microg RNA x mg(-1) cell protein). Therefore differences in protein synthesis rates, BF-2 (31.3 +/- 1.8)>RTP (25.1 +/- 1.7)>CHSE 214 (17.6 +/-1.1), were attributable to RNA translational efficiency. The most translationally efficient RNA (BF-2 cells), 1.8 mg protein synthesised x microg(-1) RNA x day(-1), corresponded to the lowest RNA half-life, 75.4 +/- 6.4 h. Translationally efficient RNA was also energetically efficient with BF-2 cells exploiting the least costly route of nucleotide supply (i.e. exogenous salvage) 3.5-6.0 times more than the least translationally efficient RNA (CHSE 214 cells). These data suggest that differential nucleotide supply, between intracellular synthesis and exogenous salvage, constitutes the area of pre-translational flexibility exploited to maintain RNA synthesis as a fixed energetic cost component of protein synthesis.

  13. Improving the efficiency of single and multiple teleportation protocols based on the direct use of partially entangled states

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

    Fortes, Raphael; Rigolin, Gustavo, E-mail: rigolin@ifi.unicamp.br

    We push the limits of the direct use of partially pure entangled states to perform quantum teleportation by presenting several protocols in many different scenarios that achieve the optimal efficiency possible. We review and put in a single formalism the three major strategies known to date that allow one to use partially entangled states for direct quantum teleportation (no distillation strategies permitted) and compare their efficiencies in real world implementations. We show how one can improve the efficiency of many direct teleportation protocols by combining these techniques. We then develop new teleportation protocols employing multipartite partially entangled states. The threemore » techniques are also used here in order to achieve the highest efficiency possible. Finally, we prove the upper bound for the optimal success rate for protocols based on partially entangled Bell states and show that some of the protocols here developed achieve such a bound. -- Highlights: •Optimal direct teleportation protocols using directly partially entangled states. •We put in a single formalism all strategies of direct teleportation. •We extend these techniques for multipartite partially entangle states. •We give upper bounds for the optimal efficiency of these protocols.« less

  14. A Comparison of Wavetable and FM Data Reduction Methods for Resynthesis of Musical Sounds

    NASA Astrophysics Data System (ADS)

    Horner, Andrew

    An ideal music-synthesis technique provides both high-level spectral control and efficient computation. Simple playback of recorded samples lacks spectral control, while additive sine-wave synthesis is inefficient. Wavetable and frequencymodulation synthesis, however, are two popular synthesis techniques that are very efficient and use only a few control parameters.

  15. Oxygen transport membrane based advanced power cycle with low pressure synthesis gas slip stream

    DOEpatents

    Kromer, Brian R.; Litwin, Michael M.; Kelly, Sean M.

    2016-09-27

    A method and system for generating electrical power in which a high pressure synthesis gas stream generated in a gasifier is partially oxidized in an oxygen transport membrane based reactor, expanded and thereafter, is combusted in an oxygen transport membrane based boiler. A low pressure synthesis gas slip stream is split off downstream of the expanders and used as the source of fuel in the oxygen transport membrane based partial oxidation reactors to allow the oxygen transport membrane to operate at low fuel pressures with high fuel utilization. The combustion within the boiler generates heat to raise steam to in turn generate electricity by a generator coupled to a steam turbine. The resultant flue gas can be purified to produce a carbon dioxide product.

  16. Efficient ammonia synthesis over a Ru/La0.5Ce0.5O1.75 catalyst pre-reduced at high temperature† †Electronic supplementary information (ESI) available: Detailed procedures for each method, catalytic performance, STEM-EDX images, and detailed characterizations. See DOI: 10.1039/c7sc05343f

    PubMed Central

    Ogura, Yuta; Sato, Katsutoshi; Miyahara, Shin-ichiro; Kawano, Yukiko; Toriyama, Takaaki; Yamamoto, Tomokazu; Matsumura, Syo; Hosokawa, Saburo

    2018-01-01

    Ammonia is an important feedstock for producing fertiliser and is also a potential energy carrier. However, the process currently used for ammonia synthesis, the Haber–Bosch process, consumes a huge amount of energy; therefore the development of new catalysts for synthesising ammonia at a high rate under mild conditions (low temperature and low pressure) is necessary. Here, we show that Ru/La0.5Ce0.5O1.75 pre-reduced at an unusually high temperature (650 °C) catalysed ammonia synthesis at extremely high rates under mild conditions; specifically, at a reaction temperature of 350 °C, the rates were 13.4, 31.3, and 44.4 mmol g–1 h–1 at 0.1, 1.0, and 3.0 MPa, respectively. Kinetic analysis revealed that this catalyst is free of hydrogen poisoning under the conditions tested. Electron energy loss spectroscopy combined with O2 absorption capacity measurements revealed that the reduced catalyst consisted of fine Ru particles (mean diameter < 2.0 nm) that were partially covered with partially reduced La0.5Ce0.5O1.75 and were dispersed on a thermostable support. Furthermore, Fourier transform infrared spectra measured after N2 addition to the catalyst revealed that N2 adsorption on Ru atoms that interacted directly with the reduced La0.5Ce0.5O1.75 weakened the N 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 N bond and thus promoted its cleavage, which is the rate-determining step for ammonia synthesis. Our results indicate that high-temperature pre-reduction of this catalyst, which consists of Ru supported on a thermostable composite oxide with a cubic fluorite structure and containing reducible cerium, resulted in the formation of many sites that were highly active for N2 reduction by hydrogen. PMID:29719696

  17. Interactive Synthesis of Code Level Security Rules

    DTIC Science & Technology

    2017-04-01

    Interactive Synthesis of Code-Level Security Rules A Thesis Presented by Leo St. Amour to The Department of Computer Science in partial fulfillment...of the requirements for the degree of Master of Science in Computer Science Northeastern University Boston, Massachusetts April 2017 DISTRIBUTION...Abstract of the Thesis Interactive Synthesis of Code-Level Security Rules by Leo St. Amour Master of Science in Computer Science Northeastern University

  18. Identification of Sporopollenin as the Outer Layer of Cell Wall in Microalga Chlorella protothecoides.

    PubMed

    He, Xi; Dai, Junbiao; Wu, Qingyu

    2016-01-01

    Chlorella protothecoides has been put forth as a promising candidate for commercial biodiesel production. However, the cost of biodiesel remains much higher than diesel from fossil fuel sources, partially due to the high costs of oil extraction from algae. Here, we identified the presence of a sporopollenin layer outside the polysaccharide cell wall; this was evaluated using transmission electron microscopy, 2-aminoethanol treatment, acetolysis, and Fourier Transform Infrared Spectroscopy. We also performed bioinformatics analysis of the genes of the C. protothecoides genome that are likely involved in sporopollenin synthesis, secretion, and translocation, and evaluated the expression of these genes via real-time PCR. We also found that that removal of this sporopollenin layer greatly improved the efficiency of oil extraction.

  19. Synthesis and biological evaluation of manzamine analogues.

    PubMed

    Winkler, Jeffrey D; Londregan, Allyn T; Ragains, Justin R; Hamann, Mark T

    2006-07-20

    [Structure: see text] The synthesis and biological evaluation of a series of analogues of manzamine A, representing partial structures of the pentacyclic ABCDE diamine core, is described. All new compounds were screened against Plasmodium falciparum and demonstrated attenuated antimalarial activity relative to that of manzamine A.

  20. DNA synthesis by Pol η promotes fragile site stability by preventing under-replicated DNA in mitosis

    PubMed Central

    Bergoglio, Valérie; Boyer, Anne-Sophie; Walsh, Erin; Naim, Valeria; Legube, Gaëlle; Lee, Marietta Y.W.T.; Rey, Laurie; Rosselli, Filippo; Cazaux, Christophe; Eckert, Kristin A.

    2013-01-01

    Human DNA polymerase η (Pol η) is best known for its role in responding to UV irradiation–induced genome damage. We have recently observed that Pol η is also required for the stability of common fragile sites (CFSs), whose rearrangements are considered a driving force of oncogenesis. Here, we explored the molecular mechanisms underlying this newly identified role. We demonstrated that Pol η accumulated at CFSs upon partial replication stress and could efficiently replicate non-B DNA sequences within CFSs. Pol η deficiency led to persistence of checkpoint-blind under-replicated CFS regions in mitosis, detectable as FANCD2-associated chromosomal sites that were transmitted to daughter cells in 53BP1-shielded nuclear bodies. Expression of a catalytically inactive mutant of Pol η increased replication fork stalling and activated the replication checkpoint. These data are consistent with the requirement of Pol η–dependent DNA synthesis during S phase at replication forks stalled in CFS regions to suppress CFS instability by preventing checkpoint-blind under-replicated DNA in mitosis. PMID:23609533

  1. Chitosan supramolecularly cross linked with trimesic acid - Facile synthesis, characterization and evaluation of adsorption potential for chromium(VI).

    PubMed

    Bhatt, Ronak; Sreedhar, B; Padmaja, P

    2017-11-01

    A facile synthesis of Chitosan Supramolecularly cross-linked with Trimesic Acid (CTMA) is reported in this work. The adsorption potential of CTMA for removal of hexavalent chromium was evaluated and the influence of pH, temperature, contact time and adsorbent dose on the adsorption process was investigated. The experimental results showed that CTMA could efficiently adsorb Cr 6+ and partially reduce it to the less toxic Cr 3+ state. The maximum adsorption capacity of CTMA for Cr 6+ was found to be 129.53mg/g at pH 2.0. CTMA and chromium loaded CTMA were characterised by FT-IR, Raman, TGA-DSC, SEM-EDX, XRD, ESR and XPS spectroscopic techniques. Chitosan was observed to be cross- linked with TMA via ionic, hydrogen bonding and pi-pi supramolecular interactions while adsorption of chromium onto CTMA was by electrostatic forces and hydrogen bonding. From the observed results it was evident that CTMA was successfully applied for simultaneous removal of chromium, lead and iron from chrome plating effluent. Copyright © 2017 Elsevier B.V. All rights reserved.

  2. Controllable synthesis of nitrogen-doped hollow mesoporous carbon spheres using ionic liquids as template for supercapacitors

    NASA Astrophysics Data System (ADS)

    Chen, Aibing; Li, Yunqian; Liu, Lei; Yu, Yifeng; Xia, Kechan; Wang, Yuying; Li, Shuhui

    2017-01-01

    We have demonstrated a facile and controllable synthesis of monodispersed nitrogen-doped hollow mesoporous carbon spheres (N-HMCSs) using resorcinol/formaldehyde resin as a carbon precursor, tetraethyl orthosilicate as a structure-assistant agent, ionic liquids (ILs) as soft template, partial carbon sources, and nitrogen sources. The sizes and the architectures including hollow and yolk-shell of resultant carbon spheres can be efficiently controlled through the adjustment of the content of ILs. Alkyl chain length of the ILs also has an important effect on the formation of N-HMCSs. With proper alkyl chain length and content of ILs, the resultant N-HMCSs show monodispersed hollow spheres with high surface areas (up to 1158 m2 g-1), large pore volumes (up to 1.70 cm3 g-1), and uniform mesopore size (5.0 nm). Combining the hollow mesoporous structure, high porosity, large surface area, and nitrogen functionality, the as-synthesized N-HMCSs have good supercapacitor performance with good capacitance (up to 159 F g-1) and favorable capacitance retention (88% capacitive retention after 5000 cycles).

  3. Body composition, protein and energy efficiencies, and requirements for growth of F1 Boer × Saanen goat kids.

    PubMed

    Teixeira, I A M A; Fernandes, M H M R; Filho, J M Pereira; Canesin, R C; Gomes, R A; Resende, K T

    2017-05-01

    We conducted a study in which body composition, energy and protein requirements, and efficiency of MP and ME were determined in F1 Boer × Saanen goat kids of 5 to 25 kg BW by using the comparative slaughter technique. Two experiments were performed: Exp. 1 estimated the maintenance requirements of kids from 15 to 25 kg BW, and Exp. 2 estimated the gain requirements of kids from 5 to 25 kg BW. In Exp. 1, 28 intact male F1 Boer × Saanen goat kids were utilized, with 7 kids slaughtered (BW of 15.0 ± 0.35 kg) at the onset for estimation of initial body composition and the remaining 21 kids assigned to a randomized block design. Within each block, kids were subjected to 3 levels of feed intake treatments (ad libitum [100%] or restricted to 70% or 40% ad libitum). All kids in each block were slaughtered when the animals fed ad libitum reached 25 kg BW. The NE, ME for maintenance, and partial efficiency of use of ME for NE were 321.6 kJ/kg BW, 525.9 kJ/kg BW, and 0.61, respectively. The net protein and MP for maintenance were 2.43 g/kg of BW and 4.41 g/kg of BW, respectively; thus, the estimated partial efficiency of MP for maintenance was 0.55. In Exp. 2, 32 intact male F1 Boer × Saanen goat kids were distributed in a completely randomized design and slaughtered at 5.6 ± 0.85 kg BW ( = 6), 10.0 ± 0.35 kg BW ( = 6), 15.3 ± 0.52 kg BW ( = 7), 20.4 ± 0.66 kg BW ( = 6), and 25 ± 0.46 kg BW ( = 7). Body composition was then fitted to allometric equations. Body fat composition increased from 37 to 114 g/kg empty BW (EBW; < 0.001), and body protein composition decreased by 10% (from 203.2 to 180.6 g/kg EBW; < 0.001) when kids grew from 5 to 25 kg BW. The NE increased by approximately 60% (from 7.2 to 11.5 MJ/kg of empty BW gain [EWG]; < 0.001), and the net protein for gain decreased by 10% (from 186 to 166 g/kg of EWG; < 0.001). The partial efficiency of the utilization of ME to NE for growth was 0.32 ( < 0.0001), and the partial efficiencies of the utilization of ME for the synthesis of protein and fat were 0.19 and 0.59 ( < 0.011), respectively. These results demonstrate that the protein and energy maintenance requirements in young crossbred goat kids are greater than values reported previously in feeding system studies. In addition, their requirements for gain depend on body composition and are driven by efficiencies of deposition.

  4. Highly efficient one-pot/one-step synthesis of multiblock copolymers from three-component polymerization of carbon dioxide, epoxide and lactone.

    PubMed

    Li, Yang; Hong, Jiali; Wei, Renjian; Zhang, Yingying; Tong, Zaizai; Zhang, Xinghong; Du, Binyang; Xu, Junting; Fan, Zhiqiang

    2015-02-01

    It is a long-standing challenge to combine mixed monomers into multiblock copolymer (MBC) in a one-pot/one-step polymerization manner. We report the first example of MBC with biodegradable polycarbonate and polyester blocks that were synthesized from highly efficient one-pot/one-step polymerization of cyclohexene oxide (CHO), CO 2 and ε-caprolactone (ε-CL) in the presence of zinc-cobalt double metal cyanide complex and stannous octoate. In this protocol, two cross-chain exchange reactions (CCER) occurred at dual catalysts respectively and connected two independent chain propagation procedures ( i.e. , polycarbonate formation and polyester formation) simultaneously in a block-by-block manner, affording MBC without tapering structure. The multiblock structure of MBC was determined by the rate ratio of CCER to the two chain propagations and could be simply tuned by various kinetic factors. This protocol is also of significance due to partial utilization of renewable CO 2 and improved mechanical properties of the resultant MBC.

  5. Silk fibroin scaffolds enhance cell commitment of adult rat cardiac progenitor cells.

    PubMed

    Di Felice, Valentina; Serradifalco, Claudia; Rizzuto, Luigi; De Luca, Angela; Rappa, Francesca; Barone, Rosario; Di Marco, Patrizia; Cassata, Giovanni; Puleio, Roberto; Verin, Lucia; Motta, Antonella; Migliaresi, Claudio; Guercio, Annalisa; Zummo, Giovanni

    2015-11-01

    The use of three-dimensional (3D) cultures may induce cardiac progenitor cells to synthesize their own extracellular matrix (ECM) and sarcomeric proteins to initiate cardiac differentiation. 3D cultures grown on synthetic scaffolds may favour the implantation and survival of stem cells for cell therapy when pharmacological therapies are not efficient in curing cardiovascular diseases and when organ transplantation remains the only treatment able to rescue the patient's life. Silk fibroin-based scaffolds may be used to increase cell affinity to biomaterials and may be chemically modified to improve cell adhesion. In the present study, porous, partially orientated and electrospun nanometric nets were used. Cardiac progenitor cells isolated from adult rats were seeded by capillarity in the 3D structures and cultured inside inserts for 21 days. Under this condition, the cells expressed a high level of sarcomeric and cardiac proteins and synthesized a great quantity of ECM. In particular, partially orientated scaffolds induced the synthesis of titin, which is a fundamental protein in sarcomere assembly. Copyright © 2013 John Wiley & Sons, Ltd.

  6. Neo-synthesis of estrogenic or androgenic neurosteroids determine whether long-term potentiation or depression is induced in hippocampus of male rat.

    PubMed

    Di Mauro, Michela; Tozzi, Alessandro; Calabresi, Paolo; Pettorossi, Vito Enrico; Grassi, Silvarosa

    2015-01-01

    Estrogenic and androgenic steroids synthesized in the brain may rapidly modulate synaptic plasticity interacting with specific membrane receptors. We explored by electrophysiological recordings in hippocampal slices of male rat the influence of 17β-estradiol (E2) and 5α-dihydrotestosterone (DHT) neo-synthesis on the synaptic changes induced in the CA1 region. Induction of long-term depression (LTD) and depotentiation (DP) by low frequency stimulation (LFS, 15 min-1 Hz) and of long-term potentiation (LTP) by high frequency stimulation (HFS, 1 s-100 Hz), medium (MFS, 1 s-50 Hz), or weak (WFS, 1 s-25 Hz) frequency stimulation was assayed under inhibitors of enzymes converting testosterone (T) into DHT (5α-reductase) and T into E2 (P450-aromatase). We found that LFS-LTD depends on DHT synthesis, since it was fully prevented under finasteride, an inhibitor of DHT synthesis, and rescued by exogenous DHT, while the E2 synthesis was not involved. Conversely, the full development of HFS-LTP requires the synthesis of E2, as demonstrated by the LTP reduction observed under letrozole, an inhibitor of E2 synthesis, and its full rescue by exogenous E2. For intermediate stimulation protocols DHT, but not E2 synthesis, was involved in the production of a small LTP induced by WFS, while the E2 synthesis was required for the MFS-dependent LTP. Under the combined block of DHT and E2 synthesis all stimulation frequencies induced partial LTP. Overall, these results indicate that DHT is required for converting the partial LTP into LTD whereas E2 is needed for the full expression of LTP, evidencing a key role of the neo-synthesis of sex neurosteroids in determining the direction of synaptic long-term effects.

  7. Effect of excessive acute-phase response on liver regeneration after partial hepatectomy in rats.

    PubMed

    Kusashio, Kimihiko; Shimizu, Hiroaki; Kimura, Fumio; Yoshidome, Hiroyuki; Ohtsuka, Masayuki; Kato, Atsushi; Yoshitomi, Hideyuki; Furukawa, Katsunori; Fukada, Tadaomi; Miyazaki, Masaru

    2009-01-01

    Acute-phase response (APR) is known to have a protective role against infection and tissue injury including partial hepatectomy (HTX). In this study, the effect of excessive APR on liver regeneration was investigated using a rat hepatectomized model. Experimental APR was induced by subcutaneous injection of turpentine oil, immediately, 24 h and 48 h after 50% HTX. Serum IL-6 and hepatic alpha2-macroglobulin mRNA was evaluated in rats receiving turpentine or saline as control after HTX. DNA synthesis and PCNA labeling index in the remnant liver was also investigated. Furthermore, in vitro total hepatic protein synthesis (TPS) and secretory protein synthesis (SPS) in the remnant liver were measured. Liver regeneration was significantly inhibited after HTX in the turpentine group, compared to the control. DNA synthesis and PCNA labeling index was also significantly decreased on days 1 and 2. A remarkable increase in the serum IL-6 and hepatic alpha2-macroglobulin mRNA was found in the turpentine group. Furthermore, SPS was significantly upregulated in the turpentine group, although TPS was almost similar between the groups. Induction of excessive APR after HTX inhibits liver regeneration. Acute phase protein synthesis is remarkably upregulated within the capacity of hepatic protein synthesis, most probably by a reduction in replicative protein synthesis, suggesting that APR may be more appropriate biological response for ensuring immediate survival.

  8. Quantitative proteomics revealed partial fungistatic mechanism of ammonia against conidial germination of nematode-trapping fungus Arthrobotrys oligospora ATCC24927.

    PubMed

    Liu, Tong; Tian, Dong-Wei; Zou, Li-Juan; Liu, Fang-Yu; Can, Qi-Yan; Yang, Jin-Kui; Xu, Jian-Ping; Huang, Xiao-Wei; Xi, Jia-Qin; Zhu, Ming-Liang; Mo, Ming-He; Zhang, Ke-Qin

    2018-05-01

    Ammonia is one of the fungistatic factors in soil that can suppress conidial germination, but the molecular mechanism underlying the suppression is unknown. In this study, the proteomes of fungistatic conidia, fresh conidia and germinated conidia of Arthrobotrys oligospora ATCC24927 were determined and quantified. The protein expression profile of fungistatic conidia was significantly different from those in the other two conditions. 281 proteins were down expressed in fungistatic conidia and characterized by GO annotation. Gene transcription analysis and inhibition of puromycin (a protein translation inhibitor) on conidial germination suggested that down expression of 33 protein translation related proteins might well result in repression of protein synthesis and inhibition of conidial germination. In addition, 16 down-expressed proteins were mapped to the Ras/mitogen-activated protein (Ras/MAP) regulatory networks which regulate conidial DNA synthesis. The conidial DNA synthesis was found to be definitely inhibited under by ammonia, and function studies of two Ras/MAP proteins by using knock-out strains provided partial evidence that Ras/MAP pathway regulate the conidial germination. These results suggested that down-expression of Ras/MAP related proteins might result in inhibition of DNA synthesis and finally result in inhibition conidial germination. This study revealed partial fungistatic mechanism of ammonia against conidial germination. Copyright © 2018 Elsevier Ltd. All rights reserved.

  9. Starch and the Control of Kernel Number in Maize at Low Water Potentials1

    PubMed Central

    Zinselmeier, Christopher; Jeong, Byeong-Ryong; Boyer, John S.

    1999-01-01

    After reproduction is initiated in plants, subsequent reproductive development is sometimes interrupted, which decreases the final number of seeds and fruits. We subjected maize (Zea mays L.) to low water potentials (ψw) that frequently cause this kind of failure. We observed metabolite pools and enzyme activities in the developing ovaries while we manipulated the sugar stream by feeding sucrose (Suc) to the stems. Low ψw imposed for 5 d around pollination allowed embryos to form, but abortion occurred and kernel number decreased markedly. The ovary contained starch that nearly disappeared during this abortion. Analyses showed that all of the intermediates in starch synthesis were depleted. However, when labeled Suc was fed to the stems, label arrived at the ovaries. Solute accumulated and caused osmotic adjustment. Suc accumulated, but other intermediates did not, showing that a partial block in starch synthesis occurred at the first step in Suc utilization. This step was mediated by invertase, which had low activity. Because of the block, Suc feeding only partially prevented starch disappearance and abortion. These results indicate that young embryos abort when the sugar stream is interrupted sufficiently to deplete starch during early ovary development, and this abortion results in a loss of mature seeds and fruits. At low ψw, maintaining the sugar stream partially prevented the abortion, but invertase regulated the synthesis of ovary starch and partially prevented full recovery. PMID:10482657

  10. Size-Selective Synthesis and Stabilization of Small Silver Nanoparticles on TiO 2 Partially Masked by SiO 2

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

    Bo, Zhenyu; Eaton, Todd R.; Gallagher, James R.

    Controlling metal nanoparticle size is one of the principle challenges in developing new supported catalysts. Typical methods where a metal salt is deposited and reduced can result in a polydisperse mixture of metal nanoparticles, especially at higher loading. Polydispersity can exacerbate the already significant challenge of controlling sintering at high temperatures, which decreases catalytic surface area. Here, we demonstrate the size-selective photoreduction of Ag nanoparticles on TiO2 whose surface has been partially masked with a thin SiO2 layer. To synthesize this layered oxide material, TiO2 particles are grafted with tert-butylcalix[4]arene molecular templates (~2 nm in diameter) at surface densities ofmore » 0.05–0.17 templates.nm–2, overcoated with ~2 nm of SiO2 through repeated condensation cycles of limiting amounts of tetraethoxysilane (TEOS), and the templates are removed oxidatively. Ag photodeposition results in uniform nanoparticle diameters ≤ 3.5 nm (by transmission electron microscopy (TEM)) on the partially masked TiO2, whereas Ag nanoparticles deposited on the unmodified TiO2 are larger and more polydisperse (4.7 ± 2.7 nm by TEM). Furthermore, Ag nanoparticles on the partially masked TiO2 do not sinter after heating at 450 °C for 3 h, while nanoparticles on the control surfaces sinter and grow by at least 30%, as is typical. Overall, this new synthesis approach controls metal nanoparticle dispersion and enhances thermal stability, and this facile synthesis procedure is generalizable to other TiO2-supported nanoparticles and sizes and may find use in the synthesis of new catalytic materials.« less

  11. 76 FR 38122 - Notice of Availability for Exclusive, Non-Exclusive, or Partially-Exclusive Licensing of an...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2011-06-29

    ... compounds have radical curative antimalarial activity. Brenda S. Bowen, Army Federal Register Liaison... Guanidylimidazoline Derivatives as Antimalarial Agents, Synthesis of and Methods of Use Thereof AGENCY: Department of... ``Guanidylimidazole and Guanidylimidazoline Derivatives as Antimalarial Agents, Synthesis of and Methods of Use...

  12. Institute for Atom-Efficient Chemical Transformations Energy Frontier

    Science.gov Websites

    Synthesis Search Argonne ... Search Argonne Home > Institute for Atom-Efficient Chemical Transformations Synthesis Characterization Computational Studies Evaluation and Mechanisms/Catalytic Experimentation Using

  13. Simplified Application of Material Efficiency Green Metrics to Synthesis Plans: Pedagogical Case Studies Selected from "Organic Syntheses"

    ERIC Educational Resources Information Center

    Andraos, John

    2015-01-01

    This paper presents a simplified approach for the application of material efficiency metrics to linear and convergent synthesis plans encountered in organic synthesis courses. Computations are facilitated and automated using intuitively designed Microsoft Excel spreadsheets without invoking abstract mathematical formulas. The merits of this…

  14. Effect of powder compaction on radiation-thermal synthesis of lithium-titanium ferrites

    NASA Astrophysics Data System (ADS)

    Surzhikov, A. P.; Lysenko, E. N.; Vlasov, V. A.; Malyshev, A. V.; Korobeynikov, M. V.; Mikhailenko, M. A.

    2017-01-01

    Effect of powder compaction on the efficiency of thermal and radiation-thermal synthesis of lithium-substituted ferrites was investigated by X-Ray diffraction and specific magnetization analysis. It was shown that the radiation-thermal heating of compacted powder reagents mixture leads to an increase in efficiency of lithium-titanium ferrites synthesis.

  15. Non-nucleoside building blocks for copper-assisted and copper-free click chemistry for the efficient synthesis of RNA conjugates.

    PubMed

    Jayaprakash, K N; Peng, Chang Geng; Butler, David; Varghese, Jos P; Maier, Martin A; Rajeev, Kallanthottathil G; Manoharan, Muthiah

    2010-12-03

    Novel non-nucleoside alkyne monomers compatible with oligonucleotide synthesis were designed, synthesized, and efficiently incorporated into RNA and RNA analogues during solid-phase synthesis. These modifications allowed site-specific conjugation of ligands to the RNA oligonucleotides through copper-assisted (CuAAC) and copper-free strain-promoted azide-alkyne cycloaddition (SPAAC) reactions. The SPAAC click reactions of cyclooctyne-oligonucleotides with various classes of azido-functionalized ligands in solution phase and on solid phase were efficient and quantitative and occurred under mild reaction conditions. The SPAAC reaction provides a method for the synthesis of oligonucleotide-ligand conjugates uncontaminated with copper ions.

  16. Highly efficient water-mediated approach to access benzazoles: metal catalyst and base-free synthesis of 2-substituted benzimidazoles, benzoxazoles, and benzothiazoles.

    PubMed

    Bala, Manju; Verma, Praveen Kumar; Sharma, Deepika; Kumar, Neeraj; Singh, Bikram

    2015-05-01

    An efficient water-catalyzed method has been developed for the synthesis of 2-substituted benzimidazoles, benzoxazoles, and benzothiazoles in one step. The present method excludes the usage of toxic metal catalysts and bases to produce benzazoles in good to excellent yields. An efficient and versatile water-mediated method has been established for the synthesis of various 2-arylbenzazoles. The present protocol excludes the usage of any catalyst and additive provided excellent selectivities and yields with high functional group tolerance for the synthesis of 2-arylated benzimidazoles, benzoxazoles, and benzothiazoles. Benzazolones were also synthesized using similar reaction protocol.

  17. Organizational determinants of efficiency and effectiveness in mental health partial care programs.

    PubMed Central

    Schinnar, A P; Kamis-Gould, E; Delucia, N; Rothbard, A B

    1990-01-01

    The use of partial care as a treatment modality for mentally ill patients, particularly the chronically mentally ill, has greatly increased. However, research into what constitutes a "good" program has been scant. This article reports on an evaluation study of staff productivity, cost efficiency, and service effectiveness of adult partial care programs carried out in New Jersey in fiscal year 1984/1985. Five program performance indexes are developed based on comparisons of multiple measures of resources, service activities, and client outcomes. These are used to test various hypotheses regarding the effect of organizational and fiscal variables on partial care program efficiency and effectiveness. The four issues explored are: auspices, organizational complexity, service mix, and fiscal control by the state. These were found to explain about half of the variance in program performance. In addition, partial care programs demonstrating midlevel performance with regard to productivity and efficiency were observed to be the most effective, implying a possible optimal level of efficiency at which effectiveness is maximized. PMID:2113046

  18. Efficient total synthesis of (S)-14-azacamptothecin.

    PubMed

    Liu, Guan-Sai; Yao, Yuan-Shan; Xu, Peng; Wang, Shaozhong; Yao, Zhu-Jun

    2010-06-01

    An efficient total synthesis of (S)-14-azacamptothecin has been accomplished in 10 steps and 56% overall yield from 5H-pyrano[4,3-d]pyrimidine 8. A mild Hendrickson reagent-triggered intramolecular cascade cyclization, a highly enantioselective dihydroxylation, and an efficient palladium-catalyzed transformation of an O-allyl into N-allyl group are the key steps in the synthesis. This work provides a much higher overall yield than the previous achievement and shows sound flexibility for the further applications that will lead to new bioactive analogues.

  19. Nitrogen-based catalysts for the electrochemical reduction of CO2 to CO.

    PubMed

    Tornow, Claire E; Thorson, Michael R; Ma, Sichao; Gewirth, Andrew A; Kenis, Paul J A

    2012-12-05

    The synthesis and application of carbon-supported, nitrogen-based organometallic silver catalysts for the reduction of CO(2) is studied using an electrochemical flow reactor. Their performance toward the selective formation of CO is similar to the performance achieved when using Ag as the catalyst, but comparatively at much lower silver loading. Faradaic efficiencies of the organometallic catalyst are higher than 90%, which are comparable to those of Ag. Furthermore, with the addition of an amine ligand to Ag/C, the partial current density for CO increases significantly, suggesting a possible co-catalyst mechanism. Additional improvements in activity and selectivity may be achieved as greater insight is obtained on the mechanism of CO(2) reduction and on how these complexes assemble on the carbon support.

  20. 76 FR 38122 - Notice of Availability for Exclusive, Non-Exclusive, or Partially-Exclusive Licensing of an...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2011-06-29

    ... curative antimalarial activity. Brenda S. Bowen, Army Federal Register Liaison Officer. [FR Doc. 2011-16258... Derivatives as Antimalarial Agents, Synthesis of and Methods of Use Thereof AGENCY: Department of the Army, Do...-Imidazoline Derivatives as Antimalarial Agents, Synthesis and Methods of Use Thereof,'' filed on April 26...

  1. Purification, characterization, and bioinformatics studies of phosphatidic acid phosphohydrolase from Lagenaria siceraria

    USDA-ARS?s Scientific Manuscript database

    Phosphatidic acid phosphohydrolase (PAP), EC 3.1.3.4, is the penultimate step in the Kennedy pathway of triacyl glycerol (TAG) synthesis leading to the formation of diacyl glycerol (DAG), which is a key intermediate in TAG synthesis. We partially purified a soluble PAP from mid maturing seeds of bot...

  2. The C-terminal region of translesion synthesis DNA polymerase η is partially unstructured and has high conformational flexibility

    PubMed Central

    Powers, Kyle T; Washington, M Todd

    2018-01-01

    Abstract Eukaryotic DNA polymerase η catalyzes translesion synthesis of thymine dimers and 8-oxoguanines. It is comprised of a polymerase domain and a C-terminal region, both of which are required for its biological function. The C-terminal region mediates interactions with proliferating cell nuclear antigen (PCNA) and other translesion synthesis proteins such as Rev1. This region contains a ubiquitin-binding/zinc-binding (UBZ) motif and a PCNA-interacting protein (PIP) motif. Currently little structural information is available for this region of polymerase η. Using a combination of approaches—including genetic complementation assays, X-ray crystallography, Langevin dynamics simulations, and small-angle X-ray scattering—we show that the C-terminal region is partially unstructured and has high conformational flexibility. This implies that the C-terminal region acts as a flexible tether linking the polymerase domain to PCNA thereby increasing its local concentration. Such tethering would facilitate the sampling of translesion synthesis polymerases to ensure that the most appropriate one is selected to bypass the lesion. PMID:29385534

  3. Intramolecular carbolithiation of N-allyl-ynamides: an efficient entry to 1,4-dihydropyridines and pyridines - application to a formal synthesis of sarizotan.

    PubMed

    Gati, Wafa; Rammah, Mohamed M; Rammah, Mohamed B; Evano, Gwilherm

    2012-01-01

    We have developed a general synthesis of polysubstituted 1,4-dihydropyridines and pyridines based on a highly regioselective lithiation/6-endo-dig intramolecular carbolithiation from readily available N-allyl-ynamides. This reaction, which has been successfully applied to the formal synthesis of the anti-dyskinesia agent sarizotan, further extends the use of ynamides in organic synthesis and further demonstrates the synthetic efficiency of carbometallation reactions.

  4. The Global Experience of Deployment of Energy-Efficient Technologies in High-Rise Construction

    NASA Astrophysics Data System (ADS)

    Potienko, Natalia D.; Kuznetsova, Anna A.; Solyakova, Darya N.; Klyueva, Yulia E.

    2018-03-01

    The objective of this research is to examine issues related to the increasing importance of energy-efficient technologies in high-rise construction. The aim of the paper is to investigate modern approaches to building design that involve implementation of various energy-saving technologies in diverse climates and at different structural levels, including the levels of urban development, functionality, planning, construction and engineering. The research methodology is based on the comprehensive analysis of the advanced global expertise in the design and construction of energy-efficient high-rise buildings, with the examination of their positive and negative features. The research also defines the basic principles of energy-efficient architecture. Besides, it draws parallels between the climate characteristics of countries that lead in the field of energy-efficient high-rise construction, on the one hand, and the climate in Russia, on the other, which makes it possible to use the vast experience of many countries, wholly or partially. The paper also gives an analytical review of the results arrived at by implementing energy efficiency principles into high-rise architecture. The study findings determine the impact of energy-efficient technologies on high-rise architecture and planning solutions. In conclusion, the research states that, apart from aesthetic and compositional interpretation of architectural forms, an architect nowadays has to address the task of finding a synthesis between technological and architectural solutions, which requires knowledge of advanced technologies. The study findings reveal that the implementation of modern energy-efficient technologies into high-rise construction is of immediate interest and is sure to bring long-term benefits.

  5. Biomimetically inspired asymmetric total synthesis of (+)-19-dehydroxyl arisandilactone A

    NASA Astrophysics Data System (ADS)

    Han, Yi-Xin; Jiang, Yan-Long; Li, Yong; Yu, Hai-Xin; Tong, Bing-Qi; Niu, Zhe; Zhou, Shi-Jie; Liu, Song; Lan, Yu; Chen, Jia-Hua; Yang, Zhen

    2017-01-01

    Complex natural products are a proven and rich source of disease-modulating drugs and of efficient tools for the study of chemical biology and drug discovery. The architectures of complex natural products are generally considered to represent significant barriers to efficient chemical synthesis. Here we describe a concise and efficient asymmetric synthesis of 19-dehydroxyl arisandilactone A--which belongs to a family of architecturally unique, highly oxygenated nortriterpenoids isolated from the medicinal plant Schisandra arisanensis. This synthesis takes place by means of a homo-Michael reaction, a tandem retro-Michael/Michael reaction, and Cu-catalysed intramolecular cyclopropanation as key steps. The proposed mechanisms for the homo-Michael and tandem retro-Michael/Michael reactions are supported by density functional theory (DFT) calculation. The developed chemistry may find application for the synthesis of its other family members of Schisandraceae nortriterpenoids.

  6. Intramolecular carbolithiation of N-allyl-ynamides: an efficient entry to 1,4-dihydropyridines and pyridines – application to a formal synthesis of sarizotan

    PubMed Central

    Gati, Wafa; Rammah, Mohamed M; Rammah, Mohamed B

    2012-01-01

    Summary We have developed a general synthesis of polysubstituted 1,4-dihydropyridines and pyridines based on a highly regioselective lithiation/6-endo-dig intramolecular carbolithiation from readily available N-allyl-ynamides. This reaction, which has been successfully applied to the formal synthesis of the anti-dyskinesia agent sarizotan, further extends the use of ynamides in organic synthesis and further demonstrates the synthetic efficiency of carbometallation reactions. PMID:23365632

  7. An efficient chemical synthesis of nicotinamide riboside (NAR) and analogues.

    PubMed

    Tanimori, Shinji; Ohta, Takeshi; Kirihata, Mitsunori

    2002-04-22

    A simple and efficient synthesis of nicotinamide riboside (NAR) 1 and derivatives 4 and 5 via trimethylsilyl trifluoromethanesulfonate (TMSOTf)-mediated N-glycosilation followed by spontaneous deacetylation by treating with methanol is reported.

  8. Microbial protein synthesis, ruminal digestion, microbial populations, and nitrogen balance in sheep fed diets varying in forage-to-concentrate ratio and type of forage.

    PubMed

    Ramos, S; Tejido, M L; Martínez, M E; Ranilla, M J; Carro, M D

    2009-09-01

    Six ruminally and duodenally cannulated sheep were used in a partially replicated 4 x 4 Latin square to evaluate the effects of 4 diets on microbial synthesis, microbial populations, and ruminal digestion. The experimental diets had forage to concentrate ratios (F:C; DM basis) of 70:30 (HF) or 30:70 (HC) with alfalfa hay (A) or grass hay (G) as forage and were designated as HFA, HCA, HFG, and HCG. The concentrate was based on barley, gluten feed, wheat middlings, soybean meal, palmkern meal, wheat, corn, and mineral-vitamin premix in the proportions of 22, 20, 20, 13, 12, 5, 5, and 3%, respectively (as-is basis). Sheep were fed the diets at a daily rate of 56 g/kg of BW(0.75) to minimize feed selection. High-concentrate diets resulted in greater (P < 0.001) total tract apparent OM digestibility compared with HF diets, but no differences were detected in NDF digestibility. Ruminal digestibility of OM, NDF, and ADF was decreased by increasing the proportion of concentrate, but no differences between forages were detected. Compared with sheep fed HF diets, sheep receiving HC diets had less ruminal pH values and acetate proportions, but greater butyrate proportions. No differences among diets were detected in numbers of cellulolytic bacteria, but protozoa numbers were less (P = 0.004) and total bacteria numbers tended (P = 0.08) to be less for HC diets. Carboxymethylcellulase, xylanase, and amylase activities were greater for HC compared with HF diets, with A diets showing greater (P = 0.008) carboxymethylcellulase activities than G diets. Retained N ranged from 28.7 to 37.9% of N intake and was not affected by F:C (P = 0.62) or the type of forage (P = 0.31). Microbial N synthesis and its efficiency was greater (P < 0.001) for HC diets compared with HF diets. The results indicate that concentrates with low cereal content can be included in the diet of sheep up to 70% of the diet without detrimental effects on ruminal activity, microbial synthesis efficiency, and N losses.

  9. Liposome-chaperoned cell-free synthesis for the design of proteoliposomes: Implications for therapeutic delivery.

    PubMed

    Lu, Mei; Zhao, Xiaoyun; Xing, Haonan; Xun, Zhe; Yang, Tianzhi; Cai, Cuifang; Wang, Dongkai; Ding, Pingtian

    2018-04-03

    Cell-free (CF) protein synthesis has emerged as a powerful technique platform for efficient protein production in vitro. Liposomes have been widely studied as therapeutic carriers due to their biocompatibility, biodegradability, low toxicity, flexible surface manipulation, easy preparation, and higher cargo encapsulation capability. However, rapid immune clearance, insufficient targeting capacity, and poor cytoplasmic delivery efficiency substantially restrict their clinical application. The incorporation of functional membrane proteins (MPs) or peptides allows the transfer of biological properties to liposomes and imparts them with improved circulation, increased targeting, and efficient intracellular delivery. Liposome-chaperoned CF synthesis enables production of proteoliposomes in one-step reaction, which not only substantially simplifies the production procedure but also keeps protein functionality intact. Building off these observations, proteoliposomes with integrated MPs represent an excellent candidate for therapeutic delivery. In this review, we describe recent advances in CF synthesis with emphasis on detailing key factors for improving CF expression efficiency. Furthermore, we provide insights into strategies for rational design of proteoliposomal nanodelivery systems via CF synthesis. Liposome-chaperoned CF synthesis has emerged as a powerful approach for the design of recombinant proteoliposomes in one-step reaction. The incorporation of bioactive MPs or peptides into liposomes via CF synthesis can facilitate the development of proteoliposomal nanodelivery systems with improved circulation, increased targeting, and enhanced cellular delivery capacity. Moreover, by adapting lessons learned from natural delivery vehicles, novel bio-inspired proteoliposomes with enhanced delivery properties could be produced in CF systems. In this review, we first give an overview of CF synthesis with focus on enhancing protein expression in liposome-chaperoned CF systems. Furthermore, we intend to provide insight into harnessing CF-synthesized proteoliposomes for efficient therapeutic delivery. Copyright © 2018. Published by Elsevier Ltd.

  10. Neo-synthesis of estrogenic or androgenic neurosteroids determine whether long-term potentiation or depression is induced in hippocampus of male rat

    PubMed Central

    Di Mauro, Michela; Tozzi, Alessandro; Calabresi, Paolo; Pettorossi, Vito Enrico; Grassi, Silvarosa

    2015-01-01

    Estrogenic and androgenic steroids synthesized in the brain may rapidly modulate synaptic plasticity interacting with specific membrane receptors. We explored by electrophysiological recordings in hippocampal slices of male rat the influence of 17β-estradiol (E2) and 5α-dihydrotestosterone (DHT) neo-synthesis on the synaptic changes induced in the CA1 region. Induction of long-term depression (LTD) and depotentiation (DP) by low frequency stimulation (LFS, 15 min-1 Hz) and of long-term potentiation (LTP) by high frequency stimulation (HFS, 1 s-100 Hz), medium (MFS, 1 s-50 Hz), or weak (WFS, 1 s-25 Hz) frequency stimulation was assayed under inhibitors of enzymes converting testosterone (T) into DHT (5α-reductase) and T into E2 (P450-aromatase). We found that LFS-LTD depends on DHT synthesis, since it was fully prevented under finasteride, an inhibitor of DHT synthesis, and rescued by exogenous DHT, while the E2 synthesis was not involved. Conversely, the full development of HFS-LTP requires the synthesis of E2, as demonstrated by the LTP reduction observed under letrozole, an inhibitor of E2 synthesis, and its full rescue by exogenous E2. For intermediate stimulation protocols DHT, but not E2 synthesis, was involved in the production of a small LTP induced by WFS, while the E2 synthesis was required for the MFS-dependent LTP. Under the combined block of DHT and E2 synthesis all stimulation frequencies induced partial LTP. Overall, these results indicate that DHT is required for converting the partial LTP into LTD whereas E2 is needed for the full expression of LTP, evidencing a key role of the neo-synthesis of sex neurosteroids in determining the direction of synaptic long-term effects. PMID:26483631

  11. Multigram Synthesis of a Chiral Substituted Indoline Via Copper-Catalyzed Alkene Aminooxygenation.

    PubMed

    Sequeira, Fatima C; Bovino, Michael T; Chipre, Anthony J; Chemler, Sherry R

    2012-05-01

    (S)-5-Fluoro-2-(2,2,6,6-tetramethylpiperidin-1-yloxymethyl)-1-tosylindoline, a 2-methyleneoxy-substituted chiral indoline, was synthesized on multigram scale using an efficient copper-catalyzed enantioselective intramolecular alkene aminooxygenation. The synthesis is accomplished in four steps and the indoline is obtained in 89% ee (>98% after one recrystallization). Other highlights include efficient gram-scale synthesis of the (4R,5S)-di-Ph-box ligand and efficient separation of a monoallylaniline from its bis(allyl)aniline by-product by distillation under reduced pressure.

  12. Multigram Synthesis of a Chiral Substituted Indoline Via Copper-Catalyzed Alkene Aminooxygenation

    PubMed Central

    Sequeira, Fatima C.; Bovino, Michael T.; Chipre, Anthony J.

    2012-01-01

    (S)-5-Fluoro-2-(2,2,6,6-tetramethylpiperidin-1-yloxymethyl)-1-tosylindoline, a 2-methyleneoxy-substituted chiral indoline, was synthesized on multigram scale using an efficient copper-catalyzed enantioselective intramolecular alkene aminooxygenation. The synthesis is accomplished in four steps and the indoline is obtained in 89% ee (>98% after one recrystallization). Other highlights include efficient gram-scale synthesis of the (4R,5S)-di-Ph-box ligand and efficient separation of a monoallylaniline from its bis(allyl)aniline by-product by distillation under reduced pressure. PMID:22639473

  13. Fischer-Tropsch activity for non-promoted cobalt-on-alumina catalysts

    DOEpatents

    Singleton, Alan H.; Oukaci, Rachid; Goodwin, James G.

    2001-01-01

    Cobalt catalysts, and processes employing these inventive catalysts, for hydrocarbon synthesis. The inventive catalyst comprises cobalt on an alumina support and is not promoted with any noble or near noble metals. In one aspect of the invention, the alumina support preferably includes a dopant in an amount effective for increasing the activity of the inventive catalyst. The dopant is preferably a titanium dopant. In another aspect of the invention, the cobalt catalyst is preferably reduced in the presence of hydrogen at a water vapor partial pressure effective to increase the activity of the cobalt catalyst for hydrocarbon synthesis. The water vapor partial pressure is preferably in the range of from 0 to about 0.1 atmospheres.

  14. Drug Development of the Antimalarial Agent Artemisinin: Total Synthesis, Analog Synthesis, and Structure-Activity Relationship Studies

    DTIC Science & Technology

    1990-08-15

    16. SUPPLEMENTARY NOTATION 17 COSATi CODES FiELD 07 06 CROUP 03 01 SUB-GROUP IB SUBJECT TERMS (Cont/nu* on rtvtnt if ntctiwy *ne identity b ...number of requisite substituents resulted in the synthesis of ring cleaved analogs and partial structures of artemisinin: (+)-C/D, (+)-A/ B /C, (+)-A/C...in the preparation of the unstable aldehyde 2, and in commendable fashion others have employed an enol ether photo-oxygenation as entry to that

  15. Novel multi-targeted agents for Alzheimer's disease: Synthesis, biological evaluation, and molecular modeling of novel 2-[4-(4-substitutedpiperazin-1-yl)phenyl]benzimidazoles.

    PubMed

    Ozadali-Sari, Keriman; Tüylü Küçükkılınç, Tuba; Ayazgok, Beyza; Balkan, Ayla; Unsal-Tan, Oya

    2017-06-01

    The present study describes the synthesis, pharmacological evaluation (BChE/AChE inhibition, Aβ antiaggregation, and neuroprotective effects), and molecular modeling studies of novel 2-[4-(4-substitutedpiperazin-1-yl)phenyl]benzimidazole derivatives. The alkyl-substituted derivatives exhibited selective inhibition on BChE with varying efficiency. Compounds 3b and 3d were found to be the most potent inhibitors of BChE with IC 50 values of 5.18 and 5.22μM, respectively. The kinetic studies revealed that 3b is a partial non-competitive BChE inhibitor. Molecular modeling studies also showed that the alkyl-substituted derivatives were able to reach the catalytic anionic site of the BChE. The compounds with an inhibitory effect on BChE were subsequently screened for their Aβ antiaggregating and neuroprotective activities. Compounds 3a and 3b exerted a potential neuroprotective effect against H 2 O 2 and Aβ-induced cytotoxicity in SH-SY5Y cells. Collectively, 3b was found as the most promising compound for the development of multi-target directed ligands against Alzheimer's disease. Copyright © 2017 Elsevier Inc. All rights reserved.

  16. Sequence Polishing Library (SPL) v10.0

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

    Oberortner, Ernst

    The Sequence Polishing Library (SPL) is a suite of software tools in order to automate "Design for Synthesis and Assembly" workflows. Specifically: The SPL "Converter" tool converts files among the following sequence data exchange formats: CSV, FASTA, GenBank, and Synthetic Biology Open Language (SBOL); The SPL "Juggler" tool optimizes the codon usages of DNA coding sequences according to an optimization strategy, a user-specific codon usage table and genetic code. In addition, the SPL "Juggler" can translate amino acid sequences into DNA sequences.:The SPL "Polisher" verifies NA sequences against DNA synthesis constraints, such as GC content, repeating k-mers, and restriction sites.more » In case of violations, the "Polisher" reports the violations in a comprehensive manner. The "Polisher" tool can also modify the violating regions according to an optimization strategy, a user-specific codon usage table and genetic code;The SPL "Partitioner" decomposes large DNA sequences into smaller building blocks with partial overlaps that enable an efficient assembly. The "Partitioner" enables the user to configure the characteristics of the overlaps, which are mostly determined by the utilized assembly protocol, such as length, GC content, or melting temperature.« less

  17. Racemic synthesis and solid phase peptide synthesis application of the chimeric valine/leucine derivative 2-amino-3,3,4-trimethyl-pentanoic acid.

    PubMed

    Pelà, M; Del Zoppo, L; Allegri, L; Marzola, E; Ruzza, C; Calo, G; Perissutti, E; Frecentese, F; Salvadori, S; Guerrini, R

    2014-07-01

    The synthesis of non natural amino acid 2-amino-3,3,4-trimethyl-pentanoic acid (Ipv) ready for solid phase peptide synthesis has been developed. Copper (I) chloride Michael addition, followed by a Curtius rearrangement are the key steps for the lpv synthesis. The racemic valine/leucine chimeric amino acid was then successfully inserted in position 5 of neuropeptide S (NPS) and the diastereomeric mixture separated by reverse phase HPLC. The two diastereomeric NPS derivatives were tested for intracellular calcium mobilization using HEK293 cells stably expressing the mouse NPS receptor where they behaved as partial agonist and pure antagonist.

  18. Micelle-Template Synthesis of Nitrogen-Doped Mesoporous Graphene as an Efficient Metal-Free Electrocatalyst for Hydrogen Production

    NASA Astrophysics Data System (ADS)

    Huang, Xiaodan; Zhao, Yufei; Ao, Zhimin; Wang, Guoxiu

    2014-12-01

    Synthesis of mesoporous graphene materials by soft-template methods remains a great challenge, owing to the poor self-assembly capability of precursors and the severe agglomeration of graphene nanosheets. Herein, a micelle-template strategy to prepare porous graphene materials with controllable mesopores, high specific surface areas and large pore volumes is reported. By fine-tuning the synthesis parameters, the pore sizes of mesoporous graphene can be rationally controlled. Nitrogen heteroatom doping is found to remarkably render electrocatalytic properties towards hydrogen evolution reactions as a highly efficient metal-free catalyst. The synthesis strategy and the demonstration of highly efficient catalytic effect provide benchmarks for preparing well-defined mesoporous graphene materials for energy production applications.

  19. Micelle-template synthesis of nitrogen-doped mesoporous graphene as an efficient metal-free electrocatalyst for hydrogen production.

    PubMed

    Huang, Xiaodan; Zhao, Yufei; Ao, Zhimin; Wang, Guoxiu

    2014-12-19

    Synthesis of mesoporous graphene materials by soft-template methods remains a great challenge, owing to the poor self-assembly capability of precursors and the severe agglomeration of graphene nanosheets. Herein, a micelle-template strategy to prepare porous graphene materials with controllable mesopores, high specific surface areas and large pore volumes is reported. By fine-tuning the synthesis parameters, the pore sizes of mesoporous graphene can be rationally controlled. Nitrogen heteroatom doping is found to remarkably render electrocatalytic properties towards hydrogen evolution reactions as a highly efficient metal-free catalyst. The synthesis strategy and the demonstration of highly efficient catalytic effect provide benchmarks for preparing well-defined mesoporous graphene materials for energy production applications.

  20. Micelle-Template Synthesis of Nitrogen-Doped Mesoporous Graphene as an Efficient Metal-Free Electrocatalyst for Hydrogen Production

    PubMed Central

    Huang, Xiaodan; Zhao, Yufei; Ao, Zhimin; Wang, Guoxiu

    2014-01-01

    Synthesis of mesoporous graphene materials by soft-template methods remains a great challenge, owing to the poor self-assembly capability of precursors and the severe agglomeration of graphene nanosheets. Herein, a micelle-template strategy to prepare porous graphene materials with controllable mesopores, high specific surface areas and large pore volumes is reported. By fine-tuning the synthesis parameters, the pore sizes of mesoporous graphene can be rationally controlled. Nitrogen heteroatom doping is found to remarkably render electrocatalytic properties towards hydrogen evolution reactions as a highly efficient metal-free catalyst. The synthesis strategy and the demonstration of highly efficient catalytic effect provide benchmarks for preparing well-defined mesoporous graphene materials for energy production applications. PMID:25523276

  1. Efficient utilization of greenhouse gases in a gas-to-liquids process combined with CO2/steam-mixed reforming and Fe-based Fischer-Tropsch synthesis.

    PubMed

    Zhang, Chundong; Jun, Ki-Won; Ha, Kyoung-Su; Lee, Yun-Jo; Kang, Seok Chang

    2014-07-15

    Two process models for carbon dioxide utilized gas-to-liquids (GTL) process (CUGP) mainly producing light olefins and Fischer-Tropsch (F-T) synthetic oils were developed by Aspen Plus software. Both models are mainly composed of a reforming unit, an F-T synthesis unit and a recycle unit, while the main difference is the feeding point of fresh CO2. In the reforming unit, CO2 reforming and steam reforming of methane are combined together to produce syngas in flexible composition. Meanwhile, CO2 hydrogenation is conducted via reverse water gas shift on the Fe-based catalysts in the F-T synthesis unit to produce hydrocarbons. After F-T synthesis, the unreacted syngas is recycled to F-T synthesis and reforming units to enhance process efficiency. From the simulation results, it was found that the carbon efficiencies of both CUGP options were successfully improved, and total CO2 emissions were significantly reduced, compared with the conventional GTL processes. The process efficiency was sensitive to recycle ratio and more recycle seemed to be beneficial for improving process efficiency and reducing CO2 emission. However, the process efficiency was rather insensitive to split ratio (recycle to reforming unit/total recycle), and the optimum split ratio was determined to be zero.

  2. Water-Assisted Highly Efficient Synthesis of Impurity-Free Single-Walled Carbon Nanotubes

    NASA Astrophysics Data System (ADS)

    Hata, Kenji; Futaba, Don N.; Mizuno, Kohei; Namai, Tatsunori; Yumura, Motoo; Iijima, Sumio

    2004-11-01

    We demonstrate the efficient chemical vapor deposition synthesis of single-walled carbon nanotubes where the activity and lifetime of the catalysts are enhanced by water. Water-stimulated enhanced catalytic activity results in massive growth of superdense and vertically aligned nanotube forests with heights up to 2.5 millimeters that can be easily separated from the catalysts, providing nanotube material with carbon purity above 99.98%. Moreover, patterned, highly organized intrinsic nanotube structures were successfully fabricated. The water-assisted synthesis method addresses many critical problems that currently plague carbon nanotube synthesis.

  3. Dynamic Decision Making under Uncertainty and Partial Information

    DTIC Science & Technology

    2017-01-30

    order to address these problems, we investigated efficient computational methodologies for dynamic decision making under uncertainty and partial...information. In the course of this research, we developed and studied efficient simulation-based methodologies for dynamic decision making under...uncertainty and partial information; (ii) studied the application of these decision making models and methodologies to practical problems, such as those

  4. Repair of Clustered Damage and DNA Polymerase Iota.

    PubMed

    Belousova, E A; Lavrik, O I

    2015-08-01

    Multiple DNA lesions occurring within one or two turns of the DNA helix known as clustered damage are a source of double-stranded DNA breaks, which represent a serious threat to the cells. Repair of clustered lesions is accomplished in several steps. If a clustered lesion contains oxidized bases, an individual DNA lesion is repaired by the base excision repair (BER) mechanism involving a specialized DNA polymerase after excising DNA damage. Here, we investigated DNA synthesis catalyzed by DNA polymerase iota using damaged DNA templates. Two types of DNA substrates were used as model DNAs: partial DNA duplexes containing breaks of different length, and DNA duplexes containing 5-formyluracil (5-foU) and uracil as a precursor of apurinic/apyrimidinic sites (AP) in opposite DNA strands. For the first time, we showed that DNA polymerase iota is able to catalyze DNA synthesis using partial DNA duplexes having breaks of different length as substrates. In addition, we found that DNA polymerase iota could catalyze DNA synthesis during repair of clustered damage via the BER system by using both undamaged and 5-foU-containing templates. We found that hPCNA (human proliferating cell nuclear antigen) increased efficacy of DNA synthesis catalyzed by DNA polymerase iota.

  5. Partially coherent surface plasmon modes

    NASA Astrophysics Data System (ADS)

    Niconoff, G. M.; Vara, P. M.; Munoz-Lopez, J.; Juárez-Morales, J. C.; Carbajal-Dominguez, A.

    2011-04-01

    Elementary long-range plasmon modes are described assuming an exponential dependence of the refractive index in the neighbourhood of the interface dielectric-metal thin film. The study is performed using coupling mode theory. The interference between two long-range plasmon modes generated that way allows the synthesis of surface sinusoidal plasmon modes, which can be considered as completely coherent generalized plasmon modes. These sinusoidal plasmon modes are used for the synthesis of new partially coherent surface plasmon modes, which are obtained by means of an incoherent superposition of sinusoidal plasmon modes where the period of each one is considered as a random variable. The kinds of surface modes generated have an easily tuneable profile controlled by means of the probability density function associated to the period. We show that partially coherent plasmon modes have the remarkable property to control the length of propagation which is a notable feature respect to the completely coherent surface plasmon mode. The numerical simulation for sinusoidal, Bessel, Gaussian and Dark Hollow plasmon modes are presented.

  6. The timing of synthesis of proteins required for mitotic spindle and phragmoplast in partially synchronized root meristems of Vicia faba L.

    PubMed

    Olszewska, M J; Marciniak, K; Kuran, H

    1990-10-01

    After cycloheximide treatment (1 h, 2.5 micrograms/ml) protein synthesis was decreased by 70% and was partially restored after 7 h of postincubation (still 20% decrease). In partially synchronized root meristems of Vicia faba L. treated with cycloheximide at middle G2, a strong decrease of the mitotic index was observed. Exposure to the drug at late G2 did not modify the mitotic index; the changes in the phase indices suggested that the course of mitosis was blocked at prophase-metaphase/anaphase-telophase transitions. The use of indirect immunocytochemical staining of tubulin (second antibody labeled with peroxidase) made it possible to show a decreased number of cells with preprophase bands in cycloheximide-treated meristems and the mitotic spindles and phragmoplasts containing a reduced number of shortened bands of microtubules. As a result of these structural and functional disturbances, binucleate cells and polyploid nuclei were observed.

  7. Production of carbon nanotubes: Chemical vapor deposition synthesis from liquefied petroleum gas over Fe-Co-Mo tri-metallic catalyst supported on MgO

    NASA Astrophysics Data System (ADS)

    Setyopratomo, P.; Wulan, Praswasti P. D. K.; Sudibandriyo, M.

    2016-06-01

    Carbon nanotubes were produced by chemical vapor deposition method to meet the specifications for hydrogen storage. So far, the various catalyst had been studied outlining their activities, performances, and efficiencies. In this work, tri-metallic catalyst consist of Fe-Co-Mo supported on MgO was used. The catalyst was prepared by wet-impregnation method. Liquefied Petroleum Gas (LPG) was used as carbon source. The synthesis was conducted in atmospheric fixed bed reactor at reaction temperature range 750 - 850 °C for 30 minutes. The impregnation method applied in this study successfully deposed metal component on the MgO support surface. It found that the deposited metal components might partially replace Mg(OH)2 or MgO molecules in their crystal lattice. Compare to the original MgO powder; it was significant increases in pore volume and surface area has occurred during catalyst preparation stages. The size of obtained carbon nanotubes is ranging from about 10.83 nm OD/4.09 nm ID up to 21.84 nm OD/6.51 nm ID, which means that multiwall carbon nanotubes were formed during the synthesis. Yield as much as 2.35 g.CNT/g.catalyst was obtained during 30 minutes synthesis and correspond to carbon nanotubes growth rate of 0.2 μm/min. The BET surface area of the obtained carbon nanotubes is 181.13 m2/g and around 50 % of which is contributed by mesopores. Micropore with half pore width less than 1 nm contribute about 10% volume of total micro and mesopores volume of the carbon nanotubes. The existence of these micropores is very important to increase the hydrogen storage capacity of the carbon nanotubes.

  8. Disclosure Control using Partially Synthetic Data for Large-Scale Health Surveys, with Applications to CanCORS

    PubMed Central

    Loong, Bronwyn; Zaslavsky, Alan M.; He, Yulei; Harrington, David P.

    2013-01-01

    Statistical agencies have begun to partially synthesize public-use data for major surveys to protect the confidentiality of respondents’ identities and sensitive attributes, by replacing high disclosure risk and sensitive variables with multiple imputations. To date, there are few applications of synthetic data techniques to large-scale healthcare survey data. Here, we describe partial synthesis of survey data collected by CanCORS, a comprehensive observational study of the experiences, treatments, and outcomes of patients with lung or colorectal cancer in the United States. We review inferential methods for partially synthetic data, and discuss selection of high disclosure risk variables for synthesis, specification of imputation models, and identification disclosure risk assessment. We evaluate data utility by replicating published analyses and comparing results using original and synthetic data, and discuss practical issues in preserving inferential conclusions. We found that important subgroup relationships must be included in the synthetic data imputation model, to preserve the data utility of the observed data for a given analysis procedure. We conclude that synthetic CanCORS data are suited best for preliminary data analyses purposes. These methods address the requirement to share data in clinical research without compromising confidentiality. PMID:23670983

  9. Proteome Profile of Starch Granules Purified from Rice (Oryza sativa) Endosperm.

    PubMed

    Xing, Shihai; Meng, Xiaoxi; Zhou, Lihui; Mujahid, Hana; Zhao, Chunfang; Zhang, Yadong; Wang, Cailin; Peng, Zhaohua

    2016-01-01

    Starch is the most important food energy source in cereals. Many of the known enzymes involved in starch biosynthesis are partially or entirely granule-associated in the endosperm. Studying the proteome of rice starch granules is critical for us to further understand the mechanisms underlying starch biosynthesis and packaging of starch granules in rice amyloplasts, consequently for the improvement of rice grain quality. In this article, we developed a protocol to purify starch granules from mature rice endosperm and verified the quality of purified starch granules by microscopy observations, I2 staining, and Western blot analyses. In addition, we found the phenol extraction method was superior to Tris-HCl buffer extraction method with respect to the efficiency in recovery of starch granule associated proteins. LC-MS/MS analysis showed identification of already known starch granule associated proteins with high confidence. Several proteins reported to be involved in starch synthesis in prior genetic studies in plants were also shown to be enriched with starch granules, either directly or indirectly, in our studies. In addition, our results suggested that a few additional candidate proteins may also be involved in starch synthesis. Furthermore, our results indicated that some starch synthesis pathway proteins are subject to protein acetylation modification. GO analysis and KEGG pathway enrichment analysis showed that the identified proteins were mainly located in plastids and involved in carbohydrate metabolism. This study substantially advances the understanding of the starch granule associated proteome in rice and post translational regulation of some starch granule associated proteins.

  10. Application of a novel design paradigm to generate general nonpeptide combinatorial templates mimicking beta-turns: synthesis of ligands for melanocortin receptors.

    PubMed

    Webb, Thomas R; Jiang, Luyong; Sviridov, Sergey; Venegas, Ruben E; Vlaskina, Anna V; McGrath, Douglas; Tucker, John; Wang, Jian; Deschenes, Alain; Li, Rongshi

    2007-01-01

    We report the further application of a novel approach to template and ligand design by the synthesis of agonists of the melanocortin receptor. This design method uses the conserved structural data from the three-dimensional conformations of beta-turn peptides to design rigid nonpeptide templates that mimic the orientation of the main chain C-alpha atoms in a peptide beta-turn. We report details on a new synthesis of derivatives of template 1 that are useful for the synthesis of exploratory libraries. The utility of this technique is further exemplified by several iterative rounds of high-throughput synthesis and screening, which result in new partially optimized nonpeptide agonists for several melanocortin receptors.

  11. EFFECTS OF X IRRADIATION ON ENZYME SYNTHESIS DURING LIVER REGENERATION

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

    Myers, D.K.

    1962-05-01

    Twenty-four different enzymes or enzyme systems were assayed in regenerating rat liver from control and irradiated animals at various times after partial hepatectomy. X irradiation, either of the whole liver region or of an exteriorized liver lobule, interfered with the accumulation of only three of these enzymes: deoxycytidylate deaminase, thymidine phosphorylase, and NAD pyrophosphorylase. Irradiation did not affect the synthesis of related enzymes such as adenosine and guanine deaminases, and inosine and uridine phosphorylases. The effects of irradiation on enzyme synthesis in regenerating liver would appear to be highly selective. (auth)

  12. Synthesis of the diazonium (perfluoroalkyl) benzenesulfonimide monomer from Nafion monomer for proton exchange membrane fuel cells

    NASA Astrophysics Data System (ADS)

    Mei, Hua; D'Andrea, Dan; Nguyen, Tuyet-Trinh; Nworie, Chima

    2014-02-01

    One diazonium (perfluoroalkyl) benzenesulfonimide monomer, perfluoro-3, 6-dioxa-4-methyl-7-octene benzenesulfonyl imide, has been synthesized from Nafion monomer for the first time. With trifluorovinyl ether and diazonium precursors, the partially-fluorinated diazonium PFSI monomer can be polymerized and will provide chemically bonding with carbon electrode in proton exchange membrane fuel cells. A systematic study of the synthesis and characterization of this diazonium PFSI monomer has been conducted by varying reaction conditions. The optimized synthesis method has been established in the lab.

  13. The double-edged effects of annealing MgO underlayers on the efficient synthesis of single-wall carbon nanotube forests.

    PubMed

    Tsuji, Takashi; Hata, Kenji; Futaba, Don N; Sakurai, Shunsuke

    2017-11-16

    Recently, the millimetre-scale, highly efficient synthesis of single-wall carbon nanotube (SWCNT) forests from Fe catalysts has been reported through the annealing of the magnesia (MgO) underlayer. Here, we report the double-edged effects of underlayer annealing on the efficiency and structure of the SWCNT forest synthesis through a temperature-dependent examination. Our results showed that the efficiency of the SWCNT forests sharply increased with increased underlayer annealing temperatures from 600 °C up to 900 °C due to a temperature-dependent structural modification, characterized by increased grain size and reduced defects, of the MgO underlayer. Beyond this temperature, the SWCNT fraction also decreased as a result of further structural modification of the MgO underlayer. This exemplifies the double-edged effects of annealing. Specifically, for underlayer annealing below 600 °C, the catalyst subsurface diffusion was found to limit the growth efficiency, and for excessively high underlayer annealing temperatures (>900 °C), catalyst coalescence/ripening led to the formation of double-wall carbon nanotubes. As a result, three distinct regions of synthesis were observed: (i) a "low yield" region below a threshold temperature (∼600 °C); (ii) an "increased yield" region from 600 to 900 °C, and (iii) a "saturation" region above 900 °C. The efficient SWCNT forest synthesis could only occur within a specific annealing temperature window as a result of this double-edged effects of underlayer annealing.

  14. 1,2-Dicyclopropylethyne and (Cyclopropylethynyl)cyclobutane from an Efficient Synthesis of 1,2-(omega-Haloalkyl)ethynes and 1-Cycloalkyl-2-(omega-haloalkyl)ethynes (Pre Print)

    DTIC Science & Technology

    2012-02-09

    Efficient Synthesis of 1,2-(ω-Haloalkyl0ethynes and 1 -Cycloalkyl-2-(ω-haloalkyl)ethynes 5b. GRANT NUMBER (Pre Print) 5c. PROGRAM ELEMENT NUMBER...suffers from low yield as is evi- dent from the reported synthesis of 5-chloropent- 1 -yne (5, 57%)9 and 1,8-dichlorooct- 1 -yne (9, 36%).8 The synthesis ... chloropropane / 1 -bromo-4-chlorobutane is very sluggish and incomplete in THF. However, the reaction in the presence of 10 mol % Bu4NI results in an

  15. Efficient synthesis of 3-O-thia-cPA and preliminary analysis of its biological activity toward autotaxin.

    PubMed

    Tanaka, Ryo; Kato, Masaru; Suzuki, Takahiro; Nakazaki, Atsuo; Nozaki, Emi; Gotoh, Mari; Murakami-Murofushi, Kimiko; Kobayashi, Susumu

    2011-07-15

    The efficient synthesis of 3-O-thia-cPAs (4a-d), sulfur analogues of cyclic phosphatidic acid (cPA), has been achieved. The key step of the synthesis is an intramolecular Arbuzov reaction to construct the cyclic thiophosphate moiety. The present synthetic route enables the synthesis of 4a-d in only four steps from the commercially available glycidol. Preliminary biological experiments showed that 4a-d exhibited a similar inhibitory effect on autotaxin (ATX) as original cPA. Copyright © 2011 Elsevier Ltd. All rights reserved.

  16. An analysis of partial efficiencies of energy utilisation of different macronutrients by barramundi (Lates calcarifer) shows that starch restricts protein utilisation in carnivorous fish.

    PubMed

    Glencross, Brett D; Blyth, David; Bourne, Nicholas; Cheers, Susan; Irvin, Simon; Wade, Nicholas M

    2017-02-01

    This study examined the effect of including different dietary proportions of starch, protein and lipid, in diets balanced for digestible energy, on the utilisation efficiencies of dietary energy by barramundi (Lates calcarifer). Each diet was fed at one of three ration levels (satiety, 80 % of initial satiety and 60 % of initial satiety) for a 42-d period. Fish performance measures (weight gain, feed intake and feed conversion ratio) were all affected by dietary energy source. The efficiency of energy utilisation was significantly reduced in fish fed the starch diet relative to the other diets, but there were no significant effects between the other macronutrients. This reduction in efficiency of utilisation was derived from a multifactorial change in both protein and lipid utilisation. The rate of protein utilisation deteriorated as the amount of starch included in the diet increased. Lipid utilisation was most dramatically affected by inclusion levels of lipid in the diet, with diets low in lipid producing component lipid utilisation rates well above 1·3, which indicates substantial lipid synthesis from other energy sources. However, the energetic cost of lipid gain was as low as 0·65 kJ per kJ of lipid deposited, indicating that barramundi very efficiently store energy in the form of lipid, particularly from dietary starch energy. This study defines how the utilisation efficiency of dietary digestible energy by barramundi is influenced by the macronutrient source providing that energy, and that the inclusion of starch causes problems with protein utilisation in this species.

  17. Extending shikimate pathway for the production of muconic acid and its precursor salicylic acid in Escherichia coli.

    PubMed

    Lin, Yuheng; Sun, Xinxiao; Yuan, Qipeng; Yan, Yajun

    2014-05-01

    cis,cis-Muconic acid (MA) and salicylic acid (SA) are naturally-occurring organic acids having great commercial value. MA is a potential platform chemical for the manufacture of several widely-used consumer plastics; while SA is mainly used for producing pharmaceuticals (for example, aspirin and lamivudine) and skincare and haircare products. At present, MA and SA are commercially produced by organic chemical synthesis using petro-derived aromatic chemicals, such as benzene, as starting materials, which is not environmentally friendly. Here, we report a novel approach for efficient microbial production of MA via extending shikimate pathway by introducing the hybrid of an SA biosynthetic pathway with its partial degradation pathway. First, we engineered a well-developed phenylalanine producing Escherichia coli strain into an SA overproducer by introducing isochorismate synthase and isochorismate pyruvate lyase. The engineered strain is able to produce 1.2g/L of SA from simple carbon sources, which is the highest titer reported so far. Further, the partial SA degradation pathway involving salicylate 1-monoxygenase and catechol 1,2-dioxygenase is established to achieve the conversion of SA to MA. Finally, a de novo MA biosynthetic pathway is assembled by integrating the established SA biosynthesis and degradation modules. Modular optimization enables the production of up to 1.5g/L MA within 48h in shake flasks. This study not only establishes an efficient microbial platform for the production of SA and MA, but also demonstrates a generalizable pathway design strategy for the de novo biosynthesis of valuable degradation metabolites. Copyright © 2014. Published by Elsevier Inc.

  18. Tactical Synthesis Of Efficient Global Search Algorithms

    NASA Technical Reports Server (NTRS)

    Nedunuri, Srinivas; Smith, Douglas R.; Cook, William R.

    2009-01-01

    Algorithm synthesis transforms a formal specification into an efficient algorithm to solve a problem. Algorithm synthesis in Specware combines the formal specification of a problem with a high-level algorithm strategy. To derive an efficient algorithm, a developer must define operators that refine the algorithm by combining the generic operators in the algorithm with the details of the problem specification. This derivation requires skill and a deep understanding of the problem and the algorithmic strategy. In this paper we introduce two tactics to ease this process. The tactics serve a similar purpose to tactics used for determining indefinite integrals in calculus, that is suggesting possible ways to attack the problem.

  19. Contrarily to whey and high protein diets, dietary free leucine supplementation cannot reverse the lack of recovery of muscle mass after prolonged immobilization during ageing.

    PubMed

    Magne, Hugues; Savary-Auzeloux, Isabelle; Migné, Carole; Peyron, Marie-Agnès; Combaret, Lydie; Rémond, Didier; Dardevet, Dominique

    2012-04-15

    During ageing, immobilization periods increase and are partially responsible of sarcopaenia by inducing a muscle atrophy which is hardly recovered from. Immobilization-induced atrophy is due to an increase of muscle apoptotic and proteolytic processes and decreased protein synthesis. Moreover, previous data suggested that the lack of muscle mass recovery might be due to a defect in protein synthesis response during rehabilitation. This study was conducted to explore protein synthesis during reloading and leucine supplementation effect as a nutritional strategy for muscle recovery. Old rats (22–24 months old) were subjected to unilateral hindlimb casting for 8 days (I8) and allowed to recover for 10–40 days (R10–R40). They were fed a casein (±leucine) diet during the recovery. Immobilized gastrocnemius muscles atrophied by 20%, and did not recover even at R40. Amount of polyubiquitinated conjugates and chymotrypsin- and trypsin-like activities of the 26S proteasome increased. These changes paralleled an ‘anabolic resistance' of the protein synthesis at the postprandial state (decrease of protein synthesis, P-S6 and P-4E-BP1). During the recovery, proteasome activities remained elevated until R10 before complete normalization and protein synthesis was slightly increased. With free leucine supplementation during recovery, if proteasome activities were normalized earlier and protein synthesis was higher during the whole recovery, it nevertheless failed in muscle mass gain. This discrepancy could be due to a ‘desynchronization' between the leucine signal and the availability of amino acids coming from casein digestion. Thus, when supplemented with leucine-rich proteins (i.e. whey) and high protein diets, animals partially recovered the muscle mass loss.

  20. Contrarily to whey and high protein diets, dietary free leucine supplementation cannot reverse the lack of recovery of muscle mass after prolonged immobilization during ageing

    PubMed Central

    Magne, Hugues; Savary-Auzeloux, Isabelle; Migné, Carole; Peyron, Marie-Agnès; Combaret, Lydie; Rémond, Didier; Dardevet, Dominique

    2012-01-01

    During ageing, immobilization periods increase and are partially responsible of sarcopaenia by inducing a muscle atrophy which is hardly recovered from. Immobilization-induced atrophy is due to an increase of muscle apoptotic and proteolytic processes and decreased protein synthesis. Moreover, previous data suggested that the lack of muscle mass recovery might be due to a defect in protein synthesis response during rehabilitation. This study was conducted to explore protein synthesis during reloading and leucine supplementation effect as a nutritional strategy for muscle recovery. Old rats (22–24 months old) were subjected to unilateral hindlimb casting for 8 days (I8) and allowed to recover for 10–40 days (R10–R40). They were fed a casein (±leucine) diet during the recovery. Immobilized gastrocnemius muscles atrophied by 20%, and did not recover even at R40. Amount of polyubiquitinated conjugates and chymotrypsin- and trypsin-like activities of the 26S proteasome increased. These changes paralleled an ‘anabolic resistance’ of the protein synthesis at the postprandial state (decrease of protein synthesis, P-S6 and P-4E-BP1). During the recovery, proteasome activities remained elevated until R10 before complete normalization and protein synthesis was slightly increased. With free leucine supplementation during recovery, if proteasome activities were normalized earlier and protein synthesis was higher during the whole recovery, it nevertheless failed in muscle mass gain. This discrepancy could be due to a ‘desynchronization’ between the leucine signal and the availability of amino acids coming from casein digestion. Thus, when supplemented with leucine-rich proteins (i.e. whey) and high protein diets, animals partially recovered the muscle mass loss. PMID:22351629

  1. An index-based algorithm for fast on-line query processing of latent semantic analysis

    PubMed Central

    Li, Pohan; Wang, Wei

    2017-01-01

    Latent Semantic Analysis (LSA) is widely used for finding the documents whose semantic is similar to the query of keywords. Although LSA yield promising similar results, the existing LSA algorithms involve lots of unnecessary operations in similarity computation and candidate check during on-line query processing, which is expensive in terms of time cost and cannot efficiently response the query request especially when the dataset becomes large. In this paper, we study the efficiency problem of on-line query processing for LSA towards efficiently searching the similar documents to a given query. We rewrite the similarity equation of LSA combined with an intermediate value called partial similarity that is stored in a designed index called partial index. For reducing the searching space, we give an approximate form of similarity equation, and then develop an efficient algorithm for building partial index, which skips the partial similarities lower than a given threshold θ. Based on partial index, we develop an efficient algorithm called ILSA for supporting fast on-line query processing. The given query is transformed into a pseudo document vector, and the similarities between query and candidate documents are computed by accumulating the partial similarities obtained from the index nodes corresponds to non-zero entries in the pseudo document vector. Compared to the LSA algorithm, ILSA reduces the time cost of on-line query processing by pruning the candidate documents that are not promising and skipping the operations that make little contribution to similarity scores. Extensive experiments through comparison with LSA have been done, which demonstrate the efficiency and effectiveness of our proposed algorithm. PMID:28520747

  2. An index-based algorithm for fast on-line query processing of latent semantic analysis.

    PubMed

    Zhang, Mingxi; Li, Pohan; Wang, Wei

    2017-01-01

    Latent Semantic Analysis (LSA) is widely used for finding the documents whose semantic is similar to the query of keywords. Although LSA yield promising similar results, the existing LSA algorithms involve lots of unnecessary operations in similarity computation and candidate check during on-line query processing, which is expensive in terms of time cost and cannot efficiently response the query request especially when the dataset becomes large. In this paper, we study the efficiency problem of on-line query processing for LSA towards efficiently searching the similar documents to a given query. We rewrite the similarity equation of LSA combined with an intermediate value called partial similarity that is stored in a designed index called partial index. For reducing the searching space, we give an approximate form of similarity equation, and then develop an efficient algorithm for building partial index, which skips the partial similarities lower than a given threshold θ. Based on partial index, we develop an efficient algorithm called ILSA for supporting fast on-line query processing. The given query is transformed into a pseudo document vector, and the similarities between query and candidate documents are computed by accumulating the partial similarities obtained from the index nodes corresponds to non-zero entries in the pseudo document vector. Compared to the LSA algorithm, ILSA reduces the time cost of on-line query processing by pruning the candidate documents that are not promising and skipping the operations that make little contribution to similarity scores. Extensive experiments through comparison with LSA have been done, which demonstrate the efficiency and effectiveness of our proposed algorithm.

  3. Increased yield of PCR products by addition of T4 gene 32 protein to the SMART PCR cDNA synthesis system.

    PubMed

    Villalva, C; Touriol, C; Seurat, P; Trempat, P; Delsol, G; Brousset, P

    2001-07-01

    Under certain conditions, T4 gene 32 protein is known to increase the efficiency of different enzymes, such as Taq DNA polymerase, reverse transcriptase, and telomerase. In this study, we compared the efficiency of the SMART PCR cDNA synthesis kit with and without the T4 gene 32 protein. The use of this cDNA synthesis procedure, in combination with T4 gene 32 protein, increases the yield of RT-PCR products from approximately 90% to 150%. This effect is even observed for long mRNA templates and low concentrations of total RNA (25 ng). Therefore, we suggest the addition of T4 gene 32 protein in the RT-PCR mixture to increase the efficiency of cDNA synthesis, particularly in cases when low amounts of tissue are used.

  4. Industry costs and consolidation : efficiency gains and mergers in the railroad industry

    DOT National Transportation Integrated Search

    2003-06-01

    Partial deregulation of the railroad industry substantially eased regulatory impediments to consolidation. Since partial deregulation, there has been a massive consolidation of firms in the railroad industry, which has been premised on efficiency gai...

  5. A new method for the determination of very small Γγ partial widths

    NASA Astrophysics Data System (ADS)

    Cardella, Giuseppe; Acosta, Luis; Auditore, Lucrezia; Camaiani, Alberto; Filippo, Enrico De; Luca, Saverio De; Gelli, Nicla; Gnoffo, Brunilde; Favela, Francisco; Fornal, Bogdan; Lanzalone, Gaetano; Leoni, Silvia; Maiolino, Concetta; Martorana, Nunzia Simona; Nannini, Adriana; Norella, Sebastianella; Pagano, Angelo; Pagano, Emanuele Vincenzo; Papa, Massimo; Pirrone, Sara; Politi, Giuseppe; Porto, Francesco; Quattrocchi, Lucia; Rizzo, Francesca; Russotto, Paolo; Santonocito, Domenico; Trifirò, Antonio; Trimarchì, Marina

    2018-01-01

    We present a new method for the measurement of very small Γγ partial width that is important for the synthesis of elements in astrophysics. The method is based on the simultaneous detection of scattered beam, residual nucleus and decay γ rays. This method is optimized for the use of the CHIMERA detector at LNS. Experimental details are described.

  6. Identification of cis-acting elements on positive-strand subgenomic mRNA required for the synthesis of negative-strand counterpart in bovine coronavirus.

    PubMed

    Yeh, Po-Yuan; Wu, Hung-Yi

    2014-07-30

    It has been demonstrated that, in addition to genomic RNA, sgmRNA is able to serve as a template for the synthesis of the negative-strand [(-)-strand] complement. However, the cis-acting elements on the positive-strand [(+)-strand] sgmRNA required for (-)-strand sgmRNA synthesis have not yet been systematically identified. In this study, we employed real-time quantitative reverse transcription polymerase chain reaction to analyze the cis-acting elements on bovine coronavirus (BCoV) sgmRNA 7 required for the synthesis of its (-)-strand counterpart by deletion mutagenesis. The major findings are as follows. (1) Deletion of the 5'-terminal leader sequence on sgmRNA 7 decreased the synthesis of the (-)-strand sgmRNA complement. (2) Deletions of the 3' untranslated region (UTR) bulged stem-loop showed no effect on (-)-strand sgmRNA synthesis; however, deletion of the 3' UTR pseudoknot decreased the yield of (-)-strand sgmRNA. (3) Nucleotides positioned from -15 to -34 of the sgmRNA 7 3'-terminal region are required for efficient (-)-strand sgmRNA synthesis. (4) Nucleotide species at the 3'-most position (-1) of sgmRNA 7 is correlated to the efficiency of (-)-strand sgmRNA synthesis. These results together suggest, in principle, that the 5'- and 3'-terminal sequences on sgmRNA 7 harbor cis-acting elements are critical for efficient (-)-strand sgmRNA synthesis in BCoV.

  7. Green chemistry for nanoparticle synthesis.

    PubMed

    Duan, Haohong; Wang, Dingsheng; Li, Yadong

    2015-08-21

    The application of the twelve principles of green chemistry in nanoparticle synthesis is a relatively new emerging issue concerning the sustainability. This field has received great attention in recent years due to its capability to design alternative, safer, energy efficient, and less toxic routes towards synthesis. These routes have been associated with the rational utilization of various substances in the nanoparticle preparations and synthetic methods, which have been broadly discussed in this tutorial review. This article is not meant to provide an exhaustive overview of green synthesis of nanoparticles, but to present several pivotal aspects of synthesis with environmental concerns, involving the selection and evaluation of nontoxic capping and reducing agents, the choice of innocuous solvents and the development of energy-efficient synthetic methods.

  8. The Use of Aryl Hydrazide Linkers for the Solid Phase Synthesis of Chemically Modified Peptides

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

    Woo, Y; Mitchell, A R; Camarero, J A

    2006-11-03

    Since Merrifield introduced the concept of solid phase synthesis in 1963 for the rapid preparation of peptides, a large variety of different supports and resin-linkers have been developed that improve the efficiency of peptide assembly and expand the myriad of synthetically feasible peptides. The aryl hydrazide is one of the most useful resin-linkers for the synthesis of chemically modified peptides. This linker is completely stable during Boc- and Fmoc-based solid phase synthesis and yet it can be cleaved under very mild oxidative conditions. The present article reviews the use of this valuable linker for the rapid and efficient synthesis ofmore » C-terminal modified peptides, head-to-tail cyclic peptides and lipidated peptides.« less

  9. Highly efficient one-pot three-component synthesis of naphthopyran derivatives in water catalyzed by hydroxyapatite

    EPA Science Inventory

    An expeditious and efficient protocol for the synthesis of naphthopyrans has been developed that proceeds via one-pot three-component sequential reaction in water catalyzed by hydroxyapatite or sodium-modified-hydroxyapatite. The title compounds have been obtained in high yield a...

  10. Self-assembly concepts in the formation of nanostructured particles using a liquid-phase synthesis method

    NASA Astrophysics Data System (ADS)

    Nandiyanto, Asep Bayu Dani

    2016-02-01

    When synthesizing particles using a liquid-phase synthesis method, reactant components show interaction with the reaction system itself. However, current reports described successful synthesis of material with only partial information on the component-component interaction and possible self-assembly mechanism occurring during the material synthesis process. Here, self-assembly concepts in the formation of nanostructured particles are presented. Influences of self-assembly parameters (i.e., surface charge, size, and concentration of components involving the reaction) on self-organized material fabrication are described. Because understanding the interaction of the component provides significant information in regard to practical uses, this report can be relevant to further material development and fabrication.

  11. Scale-Up Synthesis and Identification of GLYX-13, a NMDAR Glycine-Site Partial Agonist for the Treatment of Major Depressive Disorder.

    PubMed

    Li, Wenchao; Liu, Jingjian; Fan, Minghua; Li, Zhongtang; Chen, Yin; Zhang, Guisen; Huang, Zhuo; Zhang, Liangren

    2018-04-24

    GLYX-13, a NMDAR glycine-site partial agonist, was discovered as a promising antidepressant with rapidly acting effects but no ketamine-like side effects. However, the reported synthetic process route had deficiencies of low yield and the use of unfriendly reagents. Here, we report a scaled-up synthesis of GLYX-13 with an overall yield of 30% on the hectogram scale with a column chromatography-free strategy, where the coupling and deprotection reaction conditions were systematically optimized. Meanwhile, the absolute configuration of precursor compound of GLYX-13 was identified by X-ray single crystal diffraction. Finally, the activity of GLYX-13 was verified in the cortical neurons of mice through whole-cell voltage-clamp technique.

  12. Salt-assistant combustion synthesis of nanocrystalline Nd{sub 2}(Zr{sub 1-x}Sn{sub x}){sub 2}O{sub 7} (0 {<=} x {<=} 1) solid solutions

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

    Tong Yuping, E-mail: huabeitong@yahoo.cn; Wang Yanping

    2009-11-15

    Nanocrystalline Nd{sub 2}(Zr{sub 1-x}Sn{sub x}){sub 2}O{sub 7} series solid solutions were prepared by a convenient salt-assisted combustion process using glycine as fuel. The samples were characterized by X-ray diffraction, Fourier transform infrared spectroscopy, Raman spectroscopy, transmission electron microscopy and high-resolution transmission electron microscopy. The results showed the Zr ion can be partially replaced by Sn ion. The partial substituted products were still single-phase solid solutions and the crystal form remained unchanged. TEM images reveal that the products are composed of well-dispersed square-shaped nanocrystals. The method provides a convenient and low-cost route for the synthesis of nanostructures of oxide materials.

  13. Toxicology: Mechanisms of deuterium oxide action, part 2. [deuterium oxide effect on growth of winter rye

    NASA Technical Reports Server (NTRS)

    Siegel, S. M.

    1973-01-01

    The metabolism of winter rye seedlings (Secale cereale, L. cv. Winter) cultured in 99.6% D2O was investigated. Compared with water grown seedlings, the protein content was much lower in the D2O cultured seedlings and the incorporation of H(3)-leucine and H(3)-phenylalanine into medium to high molecular weight proteins was partially blocked. The synthesis of the enzyme peroxidase was also reduced in the D2O plants. Seedlings cultured in D2O incorporate H(3)-thymidine into DNA, but do not take up H(3)-uridine. These results suggest that some of the toxic effects of D2O culture on higher plants can be attributed to a partial block of protein synthesis.

  14. Water-Assisted Highly Efficient Synthesis of Impurity-Free Single-Walled Carbon Nanotubes-``Super-Growth''

    NASA Astrophysics Data System (ADS)

    Hata, Kenji

    2005-03-01

    We demonstrate an extremely efficient chemical vapour deposition synthesis of single-walled carbon nanotubes where the activity and lifetime of the catalysts are enhanced by water [1]. Water-stimulated enhanced catalytic activity results in massive growth of super-dense and vertically-aligned nanotube forests with heights up to 2.5 millimeters that can be easily separated from the catalysts, providing nanotube material with carbon purity above 99.98%. Moreover, patterned highly organized intrinsic nanotube structures were successfully fabricated. The water-assisted synthesis method addresses many critical problems that currently plague carbon nanotube synthesis. [1] K. Hata, et al., Science, 306, 1362 (2004).

  15. Zeolite catalysis in the synthesis of isobutylene from hydrous ethanol

    NASA Astrophysics Data System (ADS)

    Phillips, Cory Bernard

    1999-11-01

    This work deals with the synthesis of isobutylene from a hydrous ethanol feedstock over zeolites. The synthesis is accomplished in three steps: (1) low-temperature direct ethanol conversion to ethylene on H-ZSM-5 zeolite, (2) ethylene conversion to butene products over metal-exchanged zeolites, and (3) butene skeletal rearrangement to isobutylene over FER zeolites. The key to understanding and optimizing each synthesis step lies in the ability to control and regulate the zeolite acidity (Bronsted and Lewis)---both strength and number. Therefore, the continuous temperature programmed amine desorption (CTPAD) technique was further developed to simultaneously count the Bronsted acid sites and quantitatively characterize their strength. The adsorption of ethanol, reaction products, amines, coke and ethanol-derived residue (EDR) were monitored gravimetrically using the highly sensitive, novel Tapered Element Oscillating Microreactor (TEOM) apparatus. The TEOM was also used also in conjunction with CTPAD to characterize Bronsted acidity which is a new application for the instrument. For the first synthesis step, a parallel reaction exists which simultaneously produces diethyl ether and ethylene directly over H-ZSM-5. The reaction rates for each pathway were measured directly using a differential reactor operating at low temperatures (<473 K). Water in the ethanol feed enhances the rate of ethylene formation. A mechanism and kinetic expression are proposed for this reaction over H-ZSM-5, with diethyl-ether desorption and ethylene formation as the rate limiting steps. Heat of adsorption values measured from the independent microcalorimetry work reported in the literature are incorporated into the kinetic analysis which reduces the number of regressed parameters. For the remaining synthesis steps, several zeolite structures (ZSM-5, Y, FER) partially exchanged with Pd, Ti, Ni and Au were prepared and tested. It was determined from this screening study that the zeolites containing Pd are the most efficient catalysts for the dimerization reaction. Characterization results from x-ray diffraction (XRD), electron paramagnetic resonance (EPR) spectroscopy, and CTPAD suggest a stable, Pd species with a low oxidation state as part of the active site in Pd-exchanged zeolites. Isobutylene was present in the C4 fraction at reasonable quantities for most of the catalyst candidates, especially those containing an alkali metal co-cation.

  16. Repair of Ultraviolet Radiation Damage in Sensitive Mutants of Micrococcus radiodurans

    PubMed Central

    Moseley, B. E. B.

    1969-01-01

    Various aspects of the repair of ultraviolet (UV) radiation-induced damage were compared in wild-type Micrococcus radiodurans and two UV-sensitive mutants. Unlike the wild type, the mutants are more sensitive to radiation at 265 nm than at 280 nm. The delay in deoxyribonucleic acid (DNA) synthesis following exposure to UV is about seven times as long in the mutants as in the wild type. All three strains excise UV-induced pyrimidine dimers from their DNA, although the rate at which cytosine-thymine dimers are excised is slower in the mutants. The three strains also mend the single-strand breaks that appear in the irradiated DNA as a result of dimer excision, although the process is less efficient in the mutants. It is suggested that the increased sensitivity of the mutants to UV radiation may be caused by a partial defect in the second step of dimer excision. PMID:5773016

  17. Growth-dependent regulation of rRNA synthesis is mediated by a transcription initiation factor (TIF-IA).

    PubMed

    Buttgereit, D; Pflugfelder, G; Grummt, I

    1985-11-25

    Mouse RNA polymerase I requires at least two chromatographically distinct transcription factors (designated TIF-IA and TIF-IB) to initiate transcription accurately and efficiently in vitro. In this paper we describe the partial purification of TIF-IA by a four-step fractionation procedure. The amount or activity of TIF-IA fluctuates in response to the physiological state of the cells. Extracts from quiescent cells are incapable of specific transcription and do not contain detectable levels of TIF-IA. Transcriptionally inactive extracts can be restored by the addition of TIF-IA preparations that have been highly purified from exponentially growing cells. During the fractionating procedure TIF-IA co-purifies with RNA polymerase I, suggesting that it is functionally associated with the transcribing enzyme. We suggest that only those enzyme molecules that are associated with TIF-IA are capable to interact with TIF-IB and to initiate transcription.

  18. Anchoring of Cu(II) onto surface of porous metal-organic framework through post-synthesis modification for the synthesis of benzimidazoles and benzothiazoles

    NASA Astrophysics Data System (ADS)

    Kardanpour, Reihaneh; Tangestaninejad, Shahram; Mirkhani, Valiollah; Moghadam, Majid; Mohammadpoor-Baltork, Iraj; Zadehahmadi, Farnaz

    2016-03-01

    Efficient synthesis of various benzimidazoles and benzothiazoles under mild conditions catalyzed by Cu(II) anchored onto UiO-66-NH2 metal organic framework is reported. In this manner, first, the aminated UiO-66 was modified with thiophene-2-carbaldehyde and then the prepared Schiff base was reacted with CuCl2. The prepared catalyst was characterized by FT-IR, UV-vis, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), N2 adsorption, inductively coupled plasma atomic emission spectroscopy (ICP-AES) and field emission scanning electron microscopy (FE-SEM). The UiO-66-NH2-TC-Cu was applied as a highly efficient catalyst for synthesis of benzimidazole and benzothiazole derivatives by the reaction of aldehydes with 1,2-diaminobenzene or 2-aminothiophenol. The Cu(II)-containing MOF was reused several times without any appreciable loss of its efficiency.

  19. Magnetic nanoparticle supported phosphotungstic acid: An efficient catalyst for the synthesis of xanthene derivatives

    NASA Astrophysics Data System (ADS)

    Patel, Nipun; Katheriya, Deepak; Dadhania, Harsh; Dadhania, Abhishek

    2018-05-01

    Magnetic nanoparticle supported phosphotungstic acid (Fe3O4@SiO2-HPW) was applied as a highly efficient catalyst for the synthesis of 14H-dibenzoxanthene derivatives via condensation reaction of 2-naphthol and aryl aldehydes. The catalyst was found highly efficient for the synthesis of xanthene derivatives under solvent free condition. The catalyst showed high activity and stability during the reaction and provided excellent yield of the corresponding products in short reaction time. All the synthesized compounds were characterized through FT-IR, 1H-NMR and 13C-NMR spectroscopic techniques. Furthermore, the catalyst is magnetically recoverable and can be reused several times without significant loss of its catalytic activity.

  20. N-Heterocyclic carbene-catalyzed direct cross-aza-benzoin reaction: Efficient synthesis of α-amino-β-keto esters.

    PubMed

    Uno, Takuya; Kobayashi, Yusuke; Takemoto, Yoshiji

    2012-01-01

    An efficient catalytic synthesis of α-amino-β-keto esters has been newly developed. Cross-coupling of various aldehydes with α-imino ester, catalyzed by N-heterocyclic carbene, leads chemoselectively to α-amino-β-keto esters in moderate to good yields with high atom efficiency. The reaction mechanism is discussed, and it is proposed that the α-amino-β-keto esters are formed under thermodynamic control.

  1. Chemoenzymatic synthesis of new 2,4-syn-functionalized (S)-glutamate analogues and structure-activity relationship studies at ionotropic glutamate receptors and excitatory amino acid transporters.

    PubMed

    Assaf, Zeinab; Larsen, Anja P; Venskutonytė, Raminta; Han, Liwei; Abrahamsen, Bjarke; Nielsen, Birgitte; Gajhede, Michael; Kastrup, Jette S; Jensen, Anders A; Pickering, Darryl S; Frydenvang, Karla; Gefflaut, Thierry; Bunch, Lennart

    2013-02-28

    In the mammalian central nervous system, (S)-glutamate (Glu) is released from the presynaptic neuron where it activates a plethora of pre- and postsynaptic Glu receptors. The fast acting ionotropic Glu receptors (iGluRs) are ligand gated ion channels and are believed to be involved in a vast number of neurological functions such as memory and learning, synaptic plasticity, and motor function. The synthesis of 14 enantiopure 2,4-syn-Glu analogues 2b-p is accessed by a short and efficient chemoenzymatic approach starting from readily available cyclohexanone 3. Pharmacological characterization at the iGluRs and EAAT1-3 subtypes revealed analogue 2i as a selective GluK1 ligand with low nanomolar affinity. Two X-ray crystal structures of the key analogue 2i in the ligand-binding domain (LBD) of GluA2 and GluK3 were determined. Partial domain closure was seen in the GluA2-LBD complex with 2i comparable to that induced by kainate. In contrast, full domain closure was observed in the GluK3-LBD complex with 2i, similar to that of GluK3-LBD with glutamate bound.

  2. Graphene Derivative in Magnetically Recoverable Catalyst Determines Catalytic Properties in Transfer Hydrogenation of Nitroarenes to Anilines with 2-Propanol.

    PubMed

    Das, Vijay Kumar; Mazhar, Sumaira; Gregor, Lennon; Stein, Barry D; Morgan, David Gene; Maciulis, Nicholas A; Pink, Maren; Losovyj, Yaroslav; Bronstein, Lyudmila M

    2018-06-14

    Here, we report transfer hydrogenation of nitroarenes to aminoarenes using 2-propanol as a hydrogen source and Ag-containing magnetically recoverable catalysts based on partially reduced graphene oxide (pRGO) sheets. X-ray diffraction and X-ray photoelectron spectroscopy data demonstrated that, during the one-pot catalyst synthesis, formation of magnetite nanoparticles (NPs) is accompanied by the reduction of graphene oxide (GO) to pRGO. The formation of Ag 0 NPs on top of magnetite nanoparticles does not change the pRGO structure. At the same time, the catalyst structure is further modified during the transfer hydrogenation, leading to a noticeable increase of sp 2 carbons. These carbons are responsible for the adsorption of substrate and intermediates, facilitating a hydrogen transfer from Ag NPs and creating synergy between the components of the catalyst. The nitroarenes with electron withdrawing and electron donating substituents allow for excellent yields of aniline derivatives with high regio and chemoselectivity, indicating that the reaction is not disfavored by these functionalities. The versatility of the catalyst synthetic protocol was demonstrated by a synthesis of an Ru-containing graphene derivative based catalyst, also allowing for efficient transfer hydrogenation. Easy magnetic separation and stable catalyst performance in the transfer hydrogenation make this catalyst promising for future applications.

  3. Disclosure control using partially synthetic data for large-scale health surveys, with applications to CanCORS.

    PubMed

    Loong, Bronwyn; Zaslavsky, Alan M; He, Yulei; Harrington, David P

    2013-10-30

    Statistical agencies have begun to partially synthesize public-use data for major surveys to protect the confidentiality of respondents' identities and sensitive attributes by replacing high disclosure risk and sensitive variables with multiple imputations. To date, there are few applications of synthetic data techniques to large-scale healthcare survey data. Here, we describe partial synthesis of survey data collected by the Cancer Care Outcomes Research and Surveillance (CanCORS) project, a comprehensive observational study of the experiences, treatments, and outcomes of patients with lung or colorectal cancer in the USA. We review inferential methods for partially synthetic data and discuss selection of high disclosure risk variables for synthesis, specification of imputation models, and identification disclosure risk assessment. We evaluate data utility by replicating published analyses and comparing results using original and synthetic data and discuss practical issues in preserving inferential conclusions. We found that important subgroup relationships must be included in the synthetic data imputation model, to preserve the data utility of the observed data for a given analysis procedure. We conclude that synthetic CanCORS data are suited best for preliminary data analyses purposes. These methods address the requirement to share data in clinical research without compromising confidentiality. Copyright © 2013 John Wiley & Sons, Ltd.

  4. The Role of Diacylglycerol Acyltransferase (DGAT) 1 and 2 in Cardiac Metabolism and Function.

    PubMed

    Roe, Nathan D; Handzlik, Michal K; Li, Tao; Tian, Rong

    2018-03-21

    It is increasingly recognized that synthesis and turnover of cardiac triglyceride (TG) play a pivotal role in the regulation of lipid metabolism and function of the heart. The last step in TG synthesis is catalyzed by diacylglycerol:acyltransferase (DGAT) which esterifies the diacylglycerol with a fatty acid. Mammalian heart has two DGAT isoforms, DGAT1 and DGAT2, yet their roles in cardiac metabolism and function remain poorly defined. Here, we show that inactivation of DGAT1 or DGAT2 in adult mouse heart results in a moderate suppression of TG synthesis and turnover. Partial inhibition of DGAT activity increases cardiac fatty acid oxidation without affecting PPARα signaling, myocardial energetics or contractile function. Moreover, coinhibition of DGAT1/2 in the heart abrogates TG turnover and protects the heart against high fat diet-induced lipid accumulation with no adverse effects on basal or dobutamine-stimulated cardiac function. Thus, the two DGAT isoforms in the heart have partially redundant function, and pharmacological inhibition of one DGAT isoform is well tolerated in adult hearts.

  5. [Control of RNA biosynthesis in rat liver. Some features of RNA biosynthesis during prolonged protein synthesis inhibition].

    PubMed

    Todorov, I N; Shen, R A; Zheliabovskaia, S M; Galkin, A P

    1976-10-01

    A drastic inhibition of protein biosynthesis in rat liver in vivo by cycloheximide (CHI) (0.3 mg/100 g of body weight) first caused an increase of RNA synthesis (after 1 hour), which was then followed by its decrease. Partial gradual restoration of the protein synthesis level was shown to be accompanied by a repeated increase of RNA synthesis (12 hs) and its normalisation after 24 hs. The first maximum of RNA synthesis increase in the isolated nuclei system was AU-type RNA synthesis (sensitive to alpha-amanitine), the second one was due to GC-type RNA synthesis (resistant to this toxin). Purified chromatine template activity in the system with E. coli RNA polymerase (by 14%) an hour after CHI treatment, but 3 hrs later was decreased and subsequently restored (12 hrs after CHI injection). The changes of RNA biosynthesis induced by prolonged protein synthesis inhibition suggest the existence of continuous RNA synthesis control in nuclei. This control is realized by translation system using the feed back principle.

  6. Copper-catalyzed selective hydroamination reactions of alkynes

    PubMed Central

    Shi, Shi-Liang; Buchwald, Stephen L.

    2014-01-01

    The development of selective reactions that utilize easily available and abundant precursors for the efficient synthesis of amines is a longstanding goal of chemical research. Despite the centrality of amines in a number of important research areas, including medicinal chemistry, total synthesis and materials science, a general, selective, and step-efficient synthesis of amines is still needed. In this work we describe a set of mild catalytic conditions utilizing a single copper-based catalyst that enables the direct preparation of three distinct and important amine classes (enamines, α-chiral branched alkylamines, and linear alkylamines) from readily available alkyne starting materials with high levels of chemo-, regio-, and stereoselectivity. This methodology was applied to the asymmetric synthesis of rivastigmine and the formal synthesis of several other pharmaceutical agents, including duloxetine, atomoxetine, fluoxetine, and tolterodine. PMID:25515888

  7. Copper-catalysed selective hydroamination reactions of alkynes

    NASA Astrophysics Data System (ADS)

    Shi, Shi-Liang; Buchwald, Stephen L.

    2015-01-01

    The development of selective reactions that utilize easily available and abundant precursors for the efficient synthesis of amines is a long-standing goal of chemical research. Despite the centrality of amines in a number of important research areas, including medicinal chemistry, total synthesis and materials science, a general, selective and step-efficient synthesis of amines is still needed. Here, we describe a set of mild catalytic conditions utilizing a single copper-based catalyst that enables the direct preparation of three distinct and important amine classes (enamines, α-chiral branched alkylamines and linear alkylamines) from readily available alkyne starting materials with high levels of chemo-, regio- and stereoselectivity. This methodology was applied to the asymmetric synthesis of rivastigmine and the formal synthesis of several other pharmaceutical agents, including duloxetine, atomoxetine, fluoxetine and tolterodine.

  8. Anchoring of Cu(II) onto surface of porous metal-organic framework through post-synthesis modification for the synthesis of benzimidazoles and benzothiazoles

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

    Kardanpour, Reihaneh; Tangestaninejad, Shahram, E-mail: stanges@sci.ui.ac.ir; Mirkhani, Valiollah, E-mail: mirkhani@sci.ui.ac.ir

    2016-03-15

    Efficient synthesis of various benzimidazoles and benzothiazoles under mild conditions catalyzed by Cu(II) anchored onto UiO-66–NH{sub 2} metal organic framework is reported. In this manner, first, the aminated UiO-66 was modified with thiophene-2-carbaldehyde and then the prepared Schiff base was reacted with CuCl{sub 2}. The prepared catalyst was characterized by FT-IR, UV–vis, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), N{sub 2} adsorption, inductively coupled plasma atomic emission spectroscopy (ICP-AES) and field emission scanning electron microscopy (FE-SEM). The UiO-66–NH{sub 2}–TC–Cu was applied as a highly efficient catalyst for synthesis of benzimidazole and benzothiazole derivatives by the reaction of aldehydes with 1,2-diaminobenzenemore » or 2-aminothiophenol. The Cu(II)-containing MOF was reused several times without any appreciable loss of its efficiency. - Graphical abstract: Efficient synthesis of benzimidazoles and benzothiazoles catalyzed by Cu(II) anchored onto UiO-66–NH{sub 2} metal organic framework is reported. - Highlights: • A copper Schiff base was immobilized on UiO-66 via postsynthetic modification. • The modified MOFs were fully characterized by a variety of methods. • The catalyst was used for the preparation of benzimidazoles and benzothiazoles. • In comparison of other catalysts, our catalyst was more efficient and forceful.« less

  9. A comparison of Monte Carlo-based Bayesian parameter estimation methods for stochastic models of genetic networks

    PubMed Central

    Zaikin, Alexey; Míguez, Joaquín

    2017-01-01

    We compare three state-of-the-art Bayesian inference methods for the estimation of the unknown parameters in a stochastic model of a genetic network. In particular, we introduce a stochastic version of the paradigmatic synthetic multicellular clock model proposed by Ullner et al., 2007. By introducing dynamical noise in the model and assuming that the partial observations of the system are contaminated by additive noise, we enable a principled mechanism to represent experimental uncertainties in the synthesis of the multicellular system and pave the way for the design of probabilistic methods for the estimation of any unknowns in the model. Within this setup, we tackle the Bayesian estimation of a subset of the model parameters. Specifically, we compare three Monte Carlo based numerical methods for the approximation of the posterior probability density function of the unknown parameters given a set of partial and noisy observations of the system. The schemes we assess are the particle Metropolis-Hastings (PMH) algorithm, the nonlinear population Monte Carlo (NPMC) method and the approximate Bayesian computation sequential Monte Carlo (ABC-SMC) scheme. We present an extensive numerical simulation study, which shows that while the three techniques can effectively solve the problem there are significant differences both in estimation accuracy and computational efficiency. PMID:28797087

  10. An approach for fixed coefficient RNS-based FIR filter

    NASA Astrophysics Data System (ADS)

    Srinivasa Reddy, Kotha; Sahoo, Subhendu Kumar

    2017-08-01

    In this work, an efficient new modular multiplication method for {2k-1, 2k, 2k+1-1} moduli set is proposed to implement a residue number system (RNS)-based fixed coefficient finite impulse response filter. The new multiplication approach reduces the number of partial products by using pre-loaded product block. The reduction in partial products with the proposed modular multiplication improves the clock frequency and reduces the area and power as compared with the conventional modular multiplication. Further, the present approach eliminates a binary number to residue number converter circuit, which is usually needed at the front end of RNS-based system. In this work, two fixed coefficient filter architectures with the new modular multiplication approach are proposed. The filters are implemented using Verilog hardware description language. The United Microelectronics Corporation 90 nm technology library has been used for synthesis and the results area, power and delay are obtained with the help of Cadence register transfer level compiler. The power delay product (PDP) is also considered for performance comparison among the proposed filters. One of the proposed architecture is found to improve PDP gain by 60.83% as compared with the filter implemented with conventional modular multiplier. The filters functionality is validated with the help of Altera DSP Builder.

  11. Synthesis of 1-O-methylchlorogenic acid: reassignment of structure for MCGA3 isolated from bamboo (Phyllostachys edulis) leaves

    USDA-ARS?s Scientific Manuscript database

    The first synthesis of 1-O-methylchlorogenic acid is described. The short and efficient synthesis of this compound provides laboratory-scale quantities of the material to investigate its biological properties. The synthesis involved C-1 alkylation of the known (-)-4,5-cyclohexylidenequinic acid lact...

  12. Interrelationships between glutamine and citrulline metabolism.

    PubMed

    Marini, Juan C

    2016-01-01

    This article analyzes the contribution of glutamine to the synthesis of citrulline and reviews the evidence that glutamine supplementation increases citrulline production. Glutamine supplementation has been proposed in the treatment of critically ill patients; however, a recent large multicenter randomized controlled trial resulted in increased mortality in the glutamine-supplemented group. Within this context, defining the contribution of glutamine to the production of citrulline, and thus to de-novo arginine synthesis, has become a pressing issue. The beneficial effects of glutamine supplementation may be partially mediated by the effects of glutamine on citrulline synthesis by the gut and the de-novo synthesis of arginine by the kidney and other tissues. Although there is no strong evidence to support that glutamine is a major precursor for citrulline synthesis in humans, glutamine has the potential to increase overall gut function and in this way increase citrulline production.

  13. Growth, oxygen consumption, and protein and RNA synthesis rates in the yolk sac larvae of the African catfish (Clarias gariepinus).

    PubMed

    Smith, Richard W; Ottema, Colin

    2006-03-01

    Rapidly growing African catfish yolk sac larvae were investigated during the first 22 h after hatching. Body compartment protein concentration increased fourfold yet oxygen consumption remained constant (mean=21.3 +/- 3.2 nmol O2 mg(-1) protein h(-1)), suggesting fast growth results mainly from yolk sac protein absorption. The protein synthesis rates at 1-2 and 5-6 h also equaled the highest conceivable rates of muscle protein synthesis; 11.6-11.9% and 7.4-7.9% day(-1), respectively. Therefore the corresponding energetic costs of protein synthesis were almost the theoretical minimum; 13.0 +/- 1.7-16.3 +/- 2.8 micromol O2 mg(-1) protein synthesised. Total protein synthesis expenditure (74.5-77.7 micromol O2 g(-1) protein h(-1)) was also less than other yolk sac larvae. These protein synthesis rates resulted from high RNA concentrations (113.2 +/- 3.4 microg RNA mg(-1) protein) and were also correlated with RNA translational efficiency. High translational efficiency (1 h; 1.2+/-0.1 mg protein synthesised microg(-1) RNA day(-1)) equaled high synthesis rate (36.8 +/- 5.4 microg RNA microg(-1) DNA day(-1)) and both declined over 22 h. This investigation suggests rapid growth combines growth efficiency and compensatory energy partitioning. This accommodates the ontogenetic and phylogenetic standpoints imposed by energy budget limitations.

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

    Alptekin, Gokhan

    The overall objective of the proposed research is to develop a low cost, high capacity CO{sub 2} sorbent and demonstrate its technical and economic viability for pre-combustion CO{sub 2} capture. The specific objectives supporting our research plan were to optimize the chemical structure and physical properties of the sorbent, scale-up its production using high throughput manufacturing equipment and bulk raw materials and then evaluate its performance, first in bench-scale experiments and then in slipstream tests using actual coal-derived synthesis gas. One of the objectives of the laboratory-scale evaluations was to demonstrate the life and durability of the sorbent for overmore » 10,000 cycles and to assess the impact of contaminants (such as sulfur) on its performance. In the field tests, our objective was to demonstrate the operation of the sorbent using actual coal-derived synthesis gas streams generated by air-blown and oxygen-blown commercial and pilot-scale coal gasifiers (the CO{sub 2} partial pressure in these gas streams is significantly different, which directly impacts the operating conditions hence the performance of the sorbent). To support the field demonstration work, TDA collaborated with Phillips 66 and Southern Company to carry out two separate field tests using actual coal-derived synthesis gas at the Wabash River IGCC Power Plant in Terre Haute, IN and the National Carbon Capture Center (NCCC) in Wilsonville, AL. In collaboration with the University of California, Irvine (UCI), a detailed engineering and economic analysis for the new CO{sub 2} capture system was also proposed to be carried out using Aspen PlusTM simulation software, and estimate its effect on the plant efficiency.« less

  15. Decoding the Substrate Supply to Human Neuronal Nitric Oxide Synthase

    PubMed Central

    Habermeier, Alice; Closs, Ellen I.

    2013-01-01

    Nitric oxide, produced by the neuronal nitric oxide synthase (nNOS) from L-arginine is an important second messenger molecule in the central nervous system: It influences the synthesis and release of neurotransmitters and plays an important role in long-term potentiation, long-term depression and neuroendocrine secretion. However, under certain pathological conditions such as Alzheimer’s or Parkinson’s disease, stroke and multiple sclerosis, excessive NO production can lead to tissue damage. It is thus desirable to control NO production in these situations. So far, little is known about the substrate supply to human nNOS as a determinant of its activity. Measuring bioactive NO via cGMP formation in reporter cells, we demonstrate here that nNOS in both, human A673 neuroepithelioma and TGW-nu-I neuroblastoma cells can be fast and efficiently nourished by extracellular arginine that enters the cells via membrane transporters (pool I that is freely exchangeable with the extracellular space). When this pool was depleted, NO synthesis was partially sustained by intracellular arginine sources not freely exchangeable with the extracellular space (pool II). Protein breakdown made up by far the largest part of pool II in both cell types. In contrast, citrulline to arginine conversion maintained NO synthesis only in TGW-nu-I neuroblastoma, but not A673 neuroepithelioma cells. Histidine mimicked the effect of protease inhibitors causing an almost complete nNOS inhibition in cells incubated additionally in lysine that depletes the exchangeable arginine pool. Our results identify new ways to modulate nNOS activity by modifying its substrate supply. PMID:23874440

  16. Proteome Profile of Starch Granules Purified from Rice (Oryza sativa) Endosperm

    PubMed Central

    Xing, Shihai; Meng, Xiaoxi; Zhou, Lihui; Mujahid, Hana; Zhao, Chunfang; Zhang, Yadong; Wang, Cailin; Peng, Zhaohua

    2016-01-01

    Starch is the most important food energy source in cereals. Many of the known enzymes involved in starch biosynthesis are partially or entirely granule-associated in the endosperm. Studying the proteome of rice starch granules is critical for us to further understand the mechanisms underlying starch biosynthesis and packaging of starch granules in rice amyloplasts, consequently for the improvement of rice grain quality. In this article, we developed a protocol to purify starch granules from mature rice endosperm and verified the quality of purified starch granules by microscopy observations, I2 staining, and Western blot analyses. In addition, we found the phenol extraction method was superior to Tris-HCl buffer extraction method with respect to the efficiency in recovery of starch granule associated proteins. LC-MS/MS analysis showed identification of already known starch granule associated proteins with high confidence. Several proteins reported to be involved in starch synthesis in prior genetic studies in plants were also shown to be enriched with starch granules, either directly or indirectly, in our studies. In addition, our results suggested that a few additional candidate proteins may also be involved in starch synthesis. Furthermore, our results indicated that some starch synthesis pathway proteins are subject to protein acetylation modification. GO analysis and KEGG pathway enrichment analysis showed that the identified proteins were mainly located in plastids and involved in carbohydrate metabolism. This study substantially advances the understanding of the starch granule associated proteome in rice and post translational regulation of some starch granule associated proteins. PMID:27992503

  17. Method for the synthesis of chlorosilanes

    DOEpatents

    Wheeler, D.R.; Pollagi, T.P.

    1999-08-17

    A novel method is described for the synthesis of chlorinated or partially chlorinated organosilanes and organopolysilanes. The chlorination is effected by contacting an organosilanes or organopolysilanes with anhydrous CuCl{sub 2} in a nonpolar alkane solvent, preferably pentane or hexadecane, without the use of a catalyst. Copper metal, which is easily filtered, is a reaction product. The filtrate containing the chlorinated organosilane or organopolysilane can be used directly as a reactant to produce, for example, aminoorganosilanes.

  18. Method for the synthesis of chlorosilanes

    DOEpatents

    Wheeler, David R.; Pollagi, Timothy P.

    1999-01-01

    A novel method for the synthesis of chlorinated or partially chlorinated organosilanes and organopolysilanes. The chlorination is effected by contacting an organosilanes or organopolysilanes with anhydrous CuCl.sub.2 in a nonpolar alkane solvent, preferably pentane or hexadecane, without the use of a catalyst. Copper metal, which is easily filtered, is a reaction product. The filtrate containing the chlorinated organosilane or organopolysilane can be used directly as a reactant to produce, for example, aminoorganosilanes.

  19. Synthesis of ion-exchange resin for selective thorium and uranyl ions sorption

    NASA Astrophysics Data System (ADS)

    Konovalov, Konstantin; Sachkov, Victor

    2017-11-01

    In this work, the method of ion-exchange resin synthesis selective to radionuclides (uranium and thorium) is presented. The method includes synthesis of polymeric styrene-divinylbenzene macroporous matrix with size of 0.1-0.2 mm, and its subsequent transformation by nitration and then reduction by tin (II) chloride. For passivation of active primary amines partially oxidation by oxygen from air is used. Obtained ion-exchange resin has ratio of sorption sum U+Th to sorption sum of other total rare-earth elements as 1:1.88 at ratio of solid to liquid phase 1:200. The proposed method of ion-exchange resin synthesis is scaled-up for laboratory reactors with volume of 5 and 50 liters.

  20. Synthesis of Tb{sub 4}O{sub 7} complexed with reduced graphene oxide for Rhodamine-B absorption

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

    Gao, Hui, E-mail: hope@lzu.edu.cn; Zhou, Yang; Chen, Keqin

    2016-05-15

    Highlights: • Tb–rGO composite was fabricated via a facile thermally reduction process. • The green and blue emissions were both observed in the composite. • The composite exhibited efficient absorption capability for Rhodamine-B. - Abstract: Tb{sub 4}O{sub 7} complexed with reduced graphene oxide composite (Tb–rGO) had been designed and fabricated by a facile thermal reduction method. The formation of Tb{sub 4}O{sub 7} particles and reduction of graphene oxide (GO) occurred simultaneously, and partial terbium ions would be complexed with rGO via oxygen-containing function groups on rGO sheets. Introducing of terbium ions could effectively tune the photoluminescence properties of rGO, andmore » the composite exhibited the typical green emission of terbium ions as well as the blue self-luminescence of graphene entered at 440 nm. Moreover, Tb–rGO had demonstrated its high capability as an organic dye (Rhodamine-B) scavenger with high speed and efficiency. The findings showed the promising applications for large-scale removal of organic dye contaminants, especially in the field of waste water treatment.« less

  1. Peptide synthesis on glass substrate using acoustic droplet ejector.

    PubMed

    Youngki Choe; Shih-Jui Chen; Eun Sok Kim

    2014-03-01

    This paper describes the synthesis of a 9-mers-long peptide ladder structure of glycine on a modified glass surface using a nanoliter droplet ejector. To synthesize peptide on a glass substrate, SPOT peptide synthesis protocol was followed with a nozzleless acoustic droplet ejector being used to eject about 300 droplets of preactivated amino acid solution to dispense 60 nL of the solution per mer. The coupling efficiency of each mer was measured with FITC fluorescent tag to be 96%, resulting in net 70% efficiency for the whole 9-mer-long peptide of glycine. Usage of a nanoliter droplet ejector for SPOT peptide synthesis increases the density of protein array on a chip.

  2. Peptide o-aminoanilides as crypto-thioesters for protein chemical synthesis.

    PubMed

    Wang, Jia-Xing; Fang, Ge-Min; He, Yao; Qu, Da-Liang; Yu, Min; Hong, Zhang-Yong; Liu, Lei

    2015-02-09

    Fully unprotected peptide o-aminoanilides can be efficiently activated by NaNO2 in aqueous solution to furnish peptide thioesters for use in native chemical ligation. This finding enables the convergent synthesis of proteins from readily synthesizable peptide o-aminoanilides as a new type of crypto-thioesters. The practicality of this approach is shown by the synthesis of histone H2B from five peptide segments. Purification or solubilization tags, which are sometimes needed to improve the efficiency of protein chemical synthesis, can be incorporated into the o-aminoanilide moiety, as demonstrated in the preparation of the cyclic protein lactocyclicin Q. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Synthesis of a new class of Betti bases by the Mannich-type reaction: efficient, facile, solvent-free and one-pot protocol.

    PubMed

    Shahrisa, Aziz; Teimuri-Mofrad, Reza; Gholamhosseini-Nazari, Mahdi

    2015-02-01

    A variety of organocatalysts has been screened for the synthesis of arylaminonaphthols. It has been shown that (N,N-dimethylethanolamine) is a highly efficient organocatalyst for the direct synthesis of a novel class of arylaminonaphthols via three-component condensation of 2-naphthol, aldehydes, and arylamines under solvent-free conditions. Mild, one-pot, and green reaction conditions, relatively short reaction times and good yields make this protocol highly significant. 25 new compounds have been synthesized by this method.

  4. Pharmacophore mapping in the laulimalide series: total synthesis of a vinylogue for a late-stage metathesis diversification strategy.

    PubMed

    Wender, Paul A; Hilinski, Michael K; Skaanderup, Philip R; Soldermann, Nicolas G; Mooberry, Susan L

    2006-08-31

    An efficient synthesis of the macrocyclic core of laulimalide with a pendant vinyl group at C20 is described, allowing for late-stage introduction of various side chains through a selective and efficient cross metathesis diversification step. Representative analogues reported herein are the first to contain modifications to only the side chain dihydropyran of laulimalide and des-epoxy laulimalide. This step-economical strategy enables the rapid synthesis of new analogues using alkenes as an inexpensive, abundantly available diversification feedstock.

  5. Emulsion Synthesis of Size-Tunable CH3NH3PbBr3 Quantum Dots: An Alternative Route toward Efficient Light-Emitting Diodes.

    PubMed

    Huang, Hailong; Zhao, Fangchao; Liu, Lige; Zhang, Feng; Wu, Xian-gang; Shi, Lijie; Zou, Bingsuo; Pei, Qibing; Zhong, Haizheng

    2015-12-30

    We report a facile nonaqueous emulsion synthesis of colloidal halide perovskite quantum dots by controlled addition of a demulsifier into an emulsion of precursors. The size of resulting CH3NH3PbBr3 quantum dots can be tuned from 2 to 8 nm by varying the amount of demulsifier. Moreover, this emulsion synthesis also allows the purification of these quantum dots by precipitation from the colloidal solution and obtains solid-state powder which can be redissolved for thin film coating and device fabrication. The photoluminescence quantum yields of the quantum dots is generally in the range of 80-92%, and can be well-preserved after purification (∼80%). Green light-emitting diodes fabricated comprising a spin-cast layer of the colloidal CH3NH3PbBr3 quantum dots exhibited maximum current efficiency of 4.5 cd/A, power efficiency of 3.5 lm/W, and external quantum efficiency of 1.1%. This provides an alternative route toward high efficient solution-processed perovskite-based light-emitting diodes. In addition, the emulsion synthesis is versatile and can be extended for the fabrication of inorganic halide perovskite colloidal CsPbBr3 nanocrystals.

  6. A general and efficient palladium-catalyzed carbonylative synthesis of 2-aryloxazolines and 2-aryloxazines from aryl bromides.

    PubMed

    Wu, Xiao-Feng; Neumann, Helfried; Neumann, Stephan; Beller, Matthias

    2012-10-22

    Oxazoline is OK! A general and efficient method for the synthesis of oxazolines has been developed. This allowed the preparation of 27 five-membered-ring heterocycles and 11 six-membered-ring heterocycles in moderate to good yields. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Efficient Nazarov Cyclization/Wagner-Meerwein Rearrangement Terminated by a Cu(II)-Promoted Oxidation: Synthesis of 4-Alkylidene Cyclopentenones

    PubMed Central

    Lebœuf, David; Theiste, Eric; Gandon, Vincent; Daifuku, Stephanie L.; Neidig, Michael L.

    2013-01-01

    The discovery and elucidation of a novel Nazarov cyclization/Wagner-Meerwein rearrangement/oxidation sequence is described, which constitutes an efficient strategy for the synthesis of 4-alkylidene cyclopentenones. DFT computations and EPR experiments were conducted to gain further mechanistic insight into the reaction pathways. PMID:23436470

  8. l-leucine partially rescues translational and developmental defects associated with zebrafish models of Cornelia de Lange syndrome

    PubMed Central

    Xu, Baoshan; Sowa, Nenja; Cardenas, Maria E.; Gerton, Jennifer L.

    2015-01-01

    Cohesinopathies are human genetic disorders that include Cornelia de Lange syndrome (CdLS) and Roberts syndrome (RBS) and are characterized by defects in limb and craniofacial development as well as mental retardation. The developmental phenotypes of CdLS and other cohesinopathies suggest that mutations in the structure and regulation of the cohesin complex during embryogenesis interfere with gene regulation. In a previous project, we showed that RBS was associated with highly fragmented nucleoli and defects in both ribosome biogenesis and protein translation. l-leucine stimulation of the mTOR pathway partially rescued translation in human RBS cells and development in zebrafish models of RBS. In this study, we investigate protein translation in zebrafish models of CdLS. Our results show that phosphorylation of RPS6 as well as 4E-binding protein 1 (4EBP1) was reduced in nipbla/b, rad21 and smc3-morphant embryos, a pattern indicating reduced translation. Moreover, protein biosynthesis and rRNA production were decreased in the cohesin morphant embryo cells. l-leucine partly rescued protein synthesis and rRNA production in the cohesin morphants and partially restored phosphorylation of RPS6 and 4EBP1. Concomitantly, l-leucine treatment partially improved cohesinopathy embryo development including the formation of craniofacial cartilage. Interestingly, we observed that alpha-ketoisocaproate (α-KIC), which is a keto derivative of leucine, also partially rescued the development of rad21 and nipbla/b morphants by boosting mTOR-dependent translation. In summary, our results suggest that cohesinopathies are caused in part by defective protein synthesis, and stimulation of the mTOR pathway through l-leucine or its metabolite α-KIC can partially rescue development in zebrafish models for CdLS. PMID:25378554

  9. L-leucine partially rescues translational and developmental defects associated with zebrafish models of Cornelia de Lange syndrome.

    PubMed

    Xu, Baoshan; Sowa, Nenja; Cardenas, Maria E; Gerton, Jennifer L

    2015-03-15

    Cohesinopathies are human genetic disorders that include Cornelia de Lange syndrome (CdLS) and Roberts syndrome (RBS) and are characterized by defects in limb and craniofacial development as well as mental retardation. The developmental phenotypes of CdLS and other cohesinopathies suggest that mutations in the structure and regulation of the cohesin complex during embryogenesis interfere with gene regulation. In a previous project, we showed that RBS was associated with highly fragmented nucleoli and defects in both ribosome biogenesis and protein translation. l-leucine stimulation of the mTOR pathway partially rescued translation in human RBS cells and development in zebrafish models of RBS. In this study, we investigate protein translation in zebrafish models of CdLS. Our results show that phosphorylation of RPS6 as well as 4E-binding protein 1 (4EBP1) was reduced in nipbla/b, rad21 and smc3-morphant embryos, a pattern indicating reduced translation. Moreover, protein biosynthesis and rRNA production were decreased in the cohesin morphant embryo cells. l-leucine partly rescued protein synthesis and rRNA production in the cohesin morphants and partially restored phosphorylation of RPS6 and 4EBP1. Concomitantly, l-leucine treatment partially improved cohesinopathy embryo development including the formation of craniofacial cartilage. Interestingly, we observed that alpha-ketoisocaproate (α-KIC), which is a keto derivative of leucine, also partially rescued the development of rad21 and nipbla/b morphants by boosting mTOR-dependent translation. In summary, our results suggest that cohesinopathies are caused in part by defective protein synthesis, and stimulation of the mTOR pathway through l-leucine or its metabolite α-KIC can partially rescue development in zebrafish models for CdLS. © The Author 2014. Published by Oxford University Press.

  10. Efficient Classical Algorithm for Boson Sampling with Partially Distinguishable Photons

    NASA Astrophysics Data System (ADS)

    Renema, J. J.; Menssen, A.; Clements, W. R.; Triginer, G.; Kolthammer, W. S.; Walmsley, I. A.

    2018-06-01

    We demonstrate how boson sampling with photons of partial distinguishability can be expressed in terms of interference of fewer photons. We use this observation to propose a classical algorithm to simulate the output of a boson sampler fed with photons of partial distinguishability. We find conditions for which this algorithm is efficient, which gives a lower limit on the required indistinguishability to demonstrate a quantum advantage. Under these conditions, adding more photons only polynomially increases the computational cost to simulate a boson sampling experiment.

  11. Common Distribution of gad Operon in Lactobacillus brevis and its GadA Contributes to Efficient GABA Synthesis toward Cytosolic Near-Neutral pH

    PubMed Central

    Wu, Qinglong; Tun, Hein Min; Law, Yee-Song; Khafipour, Ehsan; Shah, Nagendra P.

    2017-01-01

    Many strains of lactic acid bacteria (LAB) and bifidobacteria have exhibited strain-specific capacity to produce γ-aminobutyric acid (GABA) via their glutamic acid decarboxylase (GAD) system, which is one of amino acid-dependent acid resistance (AR) systems in bacteria. However, the linkage between bacterial AR and GABA production capacity has not been well established. Meanwhile, limited evidence has been provided to the global diversity of GABA-producing LAB and bifidobacteria, and their mechanisms of efficient GABA synthesis. In this study, genomic survey identified common distribution of gad operon-encoded GAD system in Lactobacillus brevis for its GABA production among varying species of LAB and bifidobacteria. Importantly, among four commonly distributed amino acid-dependent AR systems in Lb. brevis, its GAD system was a major contributor to maintain cytosolic pH homeostasis by consuming protons via GABA synthesis. This highlights that Lb. brevis applies GAD system as the main strategy against extracellular and intracellular acidification demonstrating its high capacity of GABA production. In addition, the abundant GadA retained its activity toward near-neutral pH (pH 5.5–6.5) of cytosolic acidity thus contributing to efficient GABA synthesis in Lb. brevis. This is the first global report illustrating species-specific characteristic and mechanism of efficient GABA synthesis in Lb. brevis. PMID:28261168

  12. The Neurotrophic Substances and Behavioral Recovery from Brain Damage.

    DTIC Science & Technology

    1984-11-01

    neurotrophic substances that facilitate synthesis may be partially responsible for the com- neuronal regeneration" 12 pensatory effects of the NGF in...1962. Facilitation of simultaneous discrimination learning with strychnine sulphate. Psychopharmacologia 3: 166-172. 21. MEANS, E. D., AND D. K...34 ’- ,P ’% --- SALINE EFFECT 1071 28. SIESJO, B. K. 1981. Cell damage in the brain. A speculative synthesis . J. Cereb. Blood’ Flow Meiab. t: s155-slS5. 29

  13. Synthesis and characterization of bimetallic metal-organic framework Cu-Ru-BTC with HKUST-1 structure.

    PubMed

    Gotthardt, Meike A; Schoch, Roland; Wolf, Silke; Bauer, Matthias; Kleist, Wolfgang

    2015-02-07

    The bimetallic metal-organic framework Cu-Ru-BTC with the stoichiometric formula Cu2.75Ru0.25(BTC)2·xH2O, which is isoreticular to HKUST-1, was successfully prepared in a direct synthesis using mild reaction conditions. The partial substitution of Cu(2+) by Ru(3+) centers in the paddlewheel structure and the absence of other Ru-containing phases was proven using X-ray absorption spectroscopy.

  14. Synthesis and Properties of Rigid-Rod Benzobisazole Polymers Containing Benzothiazole Pendent Groups

    DTIC Science & Technology

    1990-11-16

    crystalline phase. Poly-p- benzamides containing bulky methyl, nitro or bromo groups affects intermolecular forces to such a large extent that lyotropic...phosphate/m- cresol . Initial attempts in our laboratory involved pendent phenylation via the synthesis of a series of phenylated terphenyl diacids and...range 2.5-9.3 dL/g and exhibited partial solubility (ə%) in m- cresol /strong acid mixtures. Concentrated solutions (>5-) could not be obtained in any

  15. One-Pot Parallel Synthesis of Lipid Library via Thiolactone Ring Opening and Screening for Gene Delivery.

    PubMed

    Molla, Mijanur R; Böser, Alexander; Rana, Akshita; Schwarz, Karina; Levkin, Pavel A

    2018-04-18

    Efficient delivery of nucleic acids into cells is of great interest in the field of cell biology and gene therapy. Despite a lot of research, transfection efficiency and structural diversity of gene-delivery vectors are still limited. A better understanding of the structure-function relationship of gene delivery vectors is also essential for the design of novel and intelligent delivery vectors, efficient in "difficult-to-transfect" cells and in vivo clinical applications. Most of the existing strategies for the synthesis of gene-delivery vectors require multiple steps and lengthy procedures. Here, we demonstrate a facile, three-component one-pot synthesis of a combinatorial library of 288 structurally diverse lipid-like molecules termed "lipidoids" via a thiolactone ring opening reaction. This strategy introduces the possibility to synthesize lipidoids with hydrophobic tails containing both unsaturated bonds and reducible disulfide groups. The whole synthesis and purification are convenient, extremely fast, and can be accomplished within a few hours. Screening of the produced lipidoids using HEK293T cells without addition of helper lipids resulted in identification of highly stable liposomes demonstrating ∼95% transfection efficiency with low toxicity.

  16. Determining the microwave coupling and operational efficiencies of a microwave plasma assisted chemical vapor deposition reactor under high pressure diamond synthesis operating conditions

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

    Nad, Shreya; Department of Physics and Astronomy, Michigan State University, East Lansing, Michigan 48824; Gu, Yajun

    2015-07-15

    The microwave coupling efficiency of the 2.45 GHz, microwave plasma assisted diamond synthesis process is investigated by experimentally measuring the performance of a specific single mode excited, internally tuned microwave plasma reactor. Plasma reactor coupling efficiencies (η) > 90% are achieved over the entire 100–260 Torr pressure range and 1.5–2.4 kW input power diamond synthesis regime. When operating at a specific experimental operating condition, small additional internal tuning adjustments can be made to achieve η > 98%. When the plasma reactor has low empty cavity losses, i.e., the empty cavity quality factor is >1500, then overall microwave discharge coupling efficienciesmore » (η{sub coup}) of >94% can be achieved. A large, safe, and efficient experimental operating regime is identified. Both substrate hot spots and the formation of microwave plasmoids are eliminated when operating within this regime. This investigation suggests that both the reactor design and the reactor process operation must be considered when attempting to lower diamond synthesis electrical energy costs while still enabling a very versatile and flexible operation performance.« less

  17. Using Decision Procedures to Build Domain-Specific Deductive Synthesis Systems

    NASA Technical Reports Server (NTRS)

    VanBaalen, Jeffrey; Roach, Steven; Lau, Sonie (Technical Monitor)

    1998-01-01

    This paper describes a class of decision procedures that we have found useful for efficient, domain-specific deductive synthesis. These procedures are called closure-based ground literal satisfiability procedures. We argue that this is a large and interesting class of procedures and show how to interface these procedures to a theorem prover for efficient deductive synthesis. Finally, we describe some results we have observed from our implementation. Amphion/NAIF is a domain-specific, high-assurance software synthesis system. It takes an abstract specification of a problem in solar system mechanics, such as 'when will a signal sent from the Cassini spacecraft to Earth be blocked by the planet Saturn?', and automatically synthesizes a FORTRAN program to solve it.

  18. Cellular recovery from exposure to sub-optimal concentrations of AB toxins that inhibit protein synthesis.

    PubMed

    Cherubin, Patrick; Quiñones, Beatriz; Teter, Ken

    2018-02-06

    Ricin, Shiga toxin, exotoxin A, and diphtheria toxin are AB-type protein toxins that act within the host cytosol and kill the host cell through pathways involving the inhibition of protein synthesis. It is thought that a single molecule of cytosolic toxin is sufficient to kill the host cell. Intoxication is therefore viewed as an irreversible process. Using flow cytometry and a fluorescent reporter system to monitor protein synthesis, we show a single molecule of cytosolic toxin is not sufficient for complete inhibition of protein synthesis or cell death. Furthermore, cells can recover from intoxication: cells with a partial loss of protein synthesis will, upon removal of the toxin, increase the level of protein production and survive the toxin challenge. Thus, in contrast to the prevailing model, ongoing toxin delivery to the cytosol appears to be required for the death of cells exposed to sub-optimal toxin concentrations.

  19. Interrelationships between glutamine and citrulline metabolism

    PubMed Central

    2015-01-01

    Purpose of review To analyze the evidence that glutamine supplementation increases citrulline production. To determine the contribution of glutamine to the synthesis of citrulline. Recent findings Glutamine supplementation has been proposed in the treatment of critically ill patients; however, a recent large multicenter randomized controlled trial resulted in increased mortality in the glutamine supplemented group. Within this context, defining the contribution of glutamine to the production of citrulline, and thus to de novo arginine synthesis, has become a pressing issue. Summary The beneficial effects of glutamine supplementation may be partially mediated by the effects of glutamine on citrulline synthesis by the gut and the de novo synthesis of arginine by the kidney and other tissues. Although there is no strong evidence to support that glutamine is a major precursor for citrulline synthesis in humans, glutamine has the potential to increase overall gut function and in this way increase citrulline production. PMID:26560519

  20. Chronological protein synthesis in regenerating rat liver.

    PubMed

    He, Jinjun; Hao, Shuai; Zhang, Hao; Guo, Fuzheng; Huang, Lingyun; Xiao, Xueyuan; He, Dacheng

    2015-07-01

    Liver regeneration has been studied for decades; however, its regulation remains unclear. In this study, we report a dynamic tracing of protein synthesis in rat regenerating liver with a new proteomic technique, (35) S in vivo labeling analysis for dynamic proteomics (SiLAD). Conventional proteomic techniques typically measure protein alteration in accumulated amounts. The SiLAD technique specifically detects protein synthesis velocity instead of accumulated amounts of protein through (35) S pulse labeling of newly synthesized proteins, providing a direct way for analyzing protein synthesis variations. Consequently, protein synthesis within short as 30 min was visualized and protein regulations in the first 8 h of regenerating liver were dynamically traced. Further, the 3.5-5 h post partial hepatectomy (PHx) was shown to be an important regulatory turning point by acute regulation of many proteins in the initiation of liver regeneration. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. A comparative study of three different synthesis routes for hydrophilic fluorophore-doped silica nanoparticles

    NASA Astrophysics Data System (ADS)

    Shahabi, Shakiba; Treccani, Laura; Rezwan, Kurosch

    2016-01-01

    The synthesis of fluorophore-doped silica nanoparticles (FDS NPs) with two conventional approaches, Stöber and microemulsion, as well as a novel amino acid-catalyzed seeds regrowth technique (ACSRT) is presented. The efficiency of each applied synthesis route toward incorporation of selected hydrophilic fluorophores, including rhodamine B isothiocyanate and fluorescein isothiocyanate, without and with an amine-containing crosslinker, into silica matrix was systematically studied. Our results clearly highlight the advantages of ACSRT to obtain FDS NPs with a remarkable encapsulation efficiency, high quantum yield, and enhanced stability against bleaching and dye leaking due to efficient embedding of the dyes inside silica network even without the amine-containing silane reagent. Moreover, evaluation of photostability of FDNPs internalized in human bone cells demonstrates the merits of ACSRT.

  2. Effects of 20-hydroxyecdysone and other hormones on egg development, and identification of a vitellin-binding protein in the ovary of the tick, Amblyomma hebraeum.

    PubMed

    Friesen, Kevin J; Kaufman, W Reuben

    2004-06-01

    Partially fed adult female Amblyomma hebraeum ticks were injected with 20-hydroxyecdysone (20E; up to 43 microg/g body weight (bw)), juvenile hormone III (JH III; up to 100 microg/g bw), bovine insulin (up to 2000 mU/g bw), or triiodothyronine (up to 200 ng/g bw) in an attempt to stimulate vitellogenesis. Of these, only 20E stimulated synthesis and release of vitellogenin (Vg). Immunoblot analysis revealed that Vg-synthesis occurred in the fat body. However, consistent with earlier observations suggesting that a distinct signal may be required for Vg-uptake, there was no significant Vg-uptake by oocytes of partially fed, 20E-treated ticks. Because Vg-uptake commonly occurs via receptor-mediated endocytosis (i.e., a specific Vg-receptor), we attempted to identify a vitellin (Vt)-binding protein in ovaries of engorged female ticks. A single 86 kDa Vt-binding protein was identified, even under reducing conditions (2-mercaptoethanol), by a ligand-blotting technique. Sodium salt of suramin (5 mM) inhibited binding of Vt to the 86 kDa protein. However, this protein was also detected in ovaries from small partially fed ticks (50-100 mg), suggesting that the inability of 20E to stimulate Vg-uptake in partially fed ticks may not have been due to the absence of a Vg-receptor.

  3. DGK1-encoded Diacylglycerol Kinase Activity Is Required for Phospholipid Synthesis during Growth Resumption from Stationary Phase in Saccharomyces cerevisiae*

    PubMed Central

    Fakas, Stylianos; Konstantinou, Chrysanthos; Carman, George M.

    2011-01-01

    In the yeast Saccharomyces cerevisiae, triacylglycerol mobilization for phospholipid synthesis occurs during growth resumption from stationary phase, and this metabolism is essential in the absence of de novo fatty acid synthesis. In this work, we provide evidence that DGK1-encoded diacylglycerol kinase activity is required to convert triacylglycerol-derived diacylglycerol to phosphatidate for phospholipid synthesis. Cells lacking diacylglycerol kinase activity (e.g. dgk1Δ mutation) failed to resume growth in the presence of the fatty acid synthesis inhibitor cerulenin. Lipid analysis data showed that dgk1Δ mutant cells did not mobilize triacylglycerol for membrane phospholipid synthesis and accumulated diacylglycerol. The dgk1Δ phenotypes were partially complemented by preventing the formation of diacylglycerol by the PAH1-encoded phosphatidate phosphatase and by channeling diacylglycerol to phosphatidylcholine via the Kennedy pathway. These observations, coupled to an inhibitory effect of dioctanoyl-diacylglycerol on the growth of wild type cells, indicated that diacylglycerol kinase also functions to alleviate diacylglycerol toxicity. PMID:21071438

  4. Studies toward brevisulcenal F via convergent strategies for marine ladder polyether synthesis.

    PubMed

    Katcher, Matthew; Jamison, Timothy F

    2018-03-15

    Shortly after the initial isolation of marine ladder polyether natural products, biomimetic epoxide-opening cascade reactions were proposed as an efficient strategy for the synthesis of these compounds. However, difficulties in assembling the cascade precursors have limited the realization of these cascades. In this report, we describe strategies that provide convergent access to cascade precursors via regioselective allylation and efficient fragment coupling. We then investigate epoxide-opening cascades promoted by strong bases for the formation of fused tetrahydropyrans. These strategies are evaluated in the context of the synthesis of rings CDEFG of brevisulcenal F.

  5. An Efficient Synthesis of de novo Imidates via Aza-Claisen Rearrangements of N-Allyl Ynamides

    PubMed Central

    DeKorver, Kyle A.; North, Troy D.; Hsung, Richard P.

    2010-01-01

    A novel thermal 3-aza-Claisen rearrangement of N-allyl ynamides for the synthesis of α-allyl imidates is described. Also, a sequential aza-Claisen, Pd-catalyzed Overman rearrangement is described for the synthesis of azapine-2-ones. PMID:21278848

  6. High-Efficiency Photovoltaic System Using Partially-Connected DC-DC Converter

    NASA Astrophysics Data System (ADS)

    Uno, Masatoshi; Kukita, Akio; Tanaka, Koji

    Power conversion electronics for photovoltaic (PV) systems are desired to operate as efficiently as possible to exploit the power generated by PV modules. This paper proposes a novel PV system in which a dc-dc converter is partially connected to series-connected PV modules. The proposed system achieves high power-conversion efficiency by reducing the passing power and input/output voltages of the converter. The theoretical operating principle was experimentally validated. Resultant efficiency performances of the proposed and conventional systems demonstrated that the proposed system was more efficient in terms of power conversion though the identical converter was used for the both systems.

  7. Synthesis of partially and fully fused polyaromatics by annulative chlorophenylene dimerization.

    PubMed

    Koga, Yoshito; Kaneda, Takeshi; Saito, Yutaro; Murakami, Kei; Itami, Kenichiro

    2018-01-26

    Since the discovery by Ullmann and Bielecki in 1901, reductive dimerization (or homocoupling) of aryl halides has been extensively exploited for the generation of a range of biaryl-based functional molecules. In contrast to the single-point connection in these products, edge-sharing fused aromatic systems have not generally been accessible from simple aryl halides via annulation cascades. Here we report a single-step synthesis of fused aromatics with a triphenylene core by the palladium-catalyzed annulative dimerization of structurally and functionally diverse chlorophenylenes through double carbon-hydrogen bond activation. The partially fused polyaromatics can be transformed into fully fused, small graphene nanoribbons, which are otherwise difficult to synthesize. This simple, yet powerful, method allows access to functional π-systems of interest in optoelectronics research. Copyright © 2018, The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works.

  8. Enhanced thermal and structural properties of partially phosphorylated polyvinyl alcohol - Aluminum phosphate (PPVA-Alpo4) nanocomposites with aluminium nitrate source

    NASA Astrophysics Data System (ADS)

    Saat, Asmalina Mohamed; Johan, Mohd Rafie

    2017-12-01

    Synthesis of AlPO4 nanocomposite depends on the ratio of aluminum to phosphate, method of synthesis and the source for aluminum and phosphate source used. Variation of phosphate and aluminum source used will form multiple equilibria reactions and affected by ions variability and concentration, stoichiometry, temperature during reaction process and especially the precipitation pH. Aluminum nitrate was used to produce a partially phosphorylated poly vinyl alcohol-aluminum phosphate (PPVA-AlPO4) nanocomposite with various nanoparticle shapes, structural and properties. Synthesis of PPVA-AlPO4 nanocomposite with aluminum nitrate shows enhancement of thermal and structural in comparison with pure PVA and modified PPVA. Thermogravimetric (TGA) analysis shows that the weight residue of PPVA-AlPO4 composite was higher than PPVA and PVA. X-ray diffraction (XRD) pattern of PVA shows a single peak broadening after the addition of phosphoric acid. Meanwhile, XRD pattern of PPVA-AlPO4 demonstrates multiple phases of AlPO4 in the nanocomposite. Field Emission Scanning Electron Microscopy (FESEM) confirmed the existence of multiple geometrical phases and nanosize of spherical particles.

  9. Timing of sperm penetration, pronuclear formation, pronuclear DNA synthesis, and first cleavage in naturally ovulated mouse eggs

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

    Krishna, M.; Generoso, W.M.

    1977-11-01

    Timing of development of naturally ovulated mouse eggs from sperm penetration to first cleavage, including that of DNA synthesis, was established. In an attempt to limit variability, partial synchronization of ovulation was accomplished by shortening the length of the dark period to five hours, and partial synchronization of sperm entry was attempted by mating the females soon after the ovulated eggs reached the ampulla and by limiting the period at which mating could occur to only 20 minutes. Evidence of sperm penetration (presence of one or more sperm in perivitelline space or inside the vitellus) was found beginning 1.75 hoursmore » after the end of the mating period. Pronuclei were formed three to four hours after sperm entry. Pronuclear DNA synthesis began about eight hours postmating, 3.25 to 4.5 hours after pronuclear formation, or about 6.25 to 8.5 hours after sperm entry; it was completed in almost all zygotes by 16 hours postmating. The first completed cleavage division was found 17 to 18 hours postmating, and almost all eggs had cleaved by 20 hours.« less

  10. Solid phase synthesis of phosphorothioate oligonucleotides utilizing diethyldithiocarbonate disulfide (DDD) as an efficient sulfur transfer reagent.

    PubMed

    Cheruvallath, Zacharia S; Kumar, R Krishna; Rentel, Claus; Cole, Douglas L; Ravikumar, Vasulinga T

    2003-04-01

    Diethyldithiodicarbonate (DDD), a cheap and easily prepared compound, is found to be a rapid and efficient sulfurizing reagent in solid phase synthesis of phosphorothioate oligodeoxyribonucleotides via the phosphoramidite approach. Product yield and quality based on IP-LC-MS compares well with high quality oligonucleotides synthesized using phenylacetyl disulfide (PADS) which is being used for manufacture of our antisense drugs.

  11. Organocatalytic sequential α-amination/Corey-Chaykovsky reaction of aldehydes: a high yield synthesis of 4-hydroxypyrazolidine derivatives.

    PubMed

    Kumar, B Senthil; Venkataramasubramanian, V; Sudalai, Arumugam

    2012-05-18

    A tandem reaction of in situ generated α-amino aldehydes with dimethyloxosulfonium methylide under Corey-Chaykovsky reaction conditions proceeds efficiently to give 4-hydroxypyrazolidine derivatives in high yields with excellent enantio- and diastereoselectivities. This organocatalytic sequential method provides for the efficient synthesis of anti-1,2-aminoalcohols, structural subunits present in several bioactive molecules as well.

  12. Efficient Nazarov cyclization/Wagner-Meerwein rearrangement terminated by a Cu(II)-promoted oxidation: synthesis of 4-alkylidene cyclopentenones.

    PubMed

    Lebœuf, David; Theiste, Eric; Gandon, Vincent; Daifuku, Stephanie L; Neidig, Michael L; Frontier, Alison J

    2013-04-08

    The discovery and elucidation of a new Nazarov cyclization/Wagner-Meerwein rearrangement/oxidation sequence is described that constitutes an efficient strategy for the synthesis of 4-alkylidene cyclopentenones. DFT computations and EPR experiments were conducted to gain further mechanistic insight into the reaction pathways. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. An efficient and highly stereoselective synthesis of new P-chiral 1,5-diphosphanylferrocene ligands and their use in enantioselective hydrogenation.

    PubMed

    Chen, Weiping; Roberts, J Stanley M; Whittall, John; Steiner, Alexander

    2006-07-21

    An efficient and highly stereoselective synthesis of P-chiral 1,5-diphosphanylferrocene ligands has been developed, and the introduction of P-chirality in ferrocene-based phosphine ligands enhances the enantioselective discrimination produced by the corresponding catalyst when matching of the planar chirality, the chirality at carbon and the chirality at phosphorus occurs.

  14. Supercritical CO2 Power Cycles: Design Considerations for Concentrating Solar Power

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

    Neises, Ty; Turchi, Craig

    2014-09-01

    A comparison of three supercritical CO2 Brayton cycles: the simple cycle, recompression cycle and partial-cooling cycle indicates the partial-cooling cycle is favored for use in concentrating solar power (CSP) systems. Although it displays slightly lower cycle efficiency versus the recompression cycle, the partial-cooling cycle is estimated to have lower total recuperator size, as well as a lower maximum s-CO2 temperature in the high-temperature recuperator. Both of these effects reduce recuperator cost. Furthermore, the partial-cooling cycle provides a larger temperature differential across the turbine, which translates into a smaller, more cost-effective thermal energy storage system. The temperature drop across the turbinemore » (and by extension, across a thermal storage system) for the partial-cooling cycle is estimated to be 23% to 35% larger compared to the recompression cycle of equal recuperator conductance between 5 and 15 MW/K. This reduces the size and cost of the thermal storage system. Simulations by NREL and Abengoa Solar indicate the partial-cooling cycle results in a lower LCOE compared with the recompression cycle, despite the former's slightly lower cycle efficiency. Advantages of the recompression cycle include higher thermal efficiency and potential for a smaller precooler. The overall impact favors the use of a partial-cooling cycle for CSP compared to the more commonly analyzed recompression cycle.« less

  15. Design and Stereoselective Preparation of a New Class of Chiral Olefin Metathesis Catalysts and Application to Enantioselective Synthesis of Quebrachamine: Catalyst Development Inspired by Natural Product Synthesis

    PubMed Central

    Sattely, Elizabeth S.; Meek, Simon J.; Malcolmson, Steven J.; Schrock, Richard R.; Hoveyda, Amir H.

    2010-01-01

    A total synthesis of the Aspidosperma alkaloid quebrachamine in racemic form is first described. A key catalytic ring-closing metathesis of an achiral triene is used to establish the all-carbon quaternary stereogenic center and the tetracyclic structure of the natural product; the catalytic transformation proceeds with reasonable efficiency through the use of existing achiral Ru or Mo catalysts. Ru- or Mo-based chiral olefin metathesis catalysts have proven to be inefficient and entirely nonselective in cases where the desired product is observed. In the present study, the synthesis route thus serves as a platform for the discovery of new olefin metathesis catalysts that allow for efficient completion of an enantioselective synthesis of quebrachamine. Accordingly, on the basis of mechanistic principles, stereogenic-at-Mo complexes bearing only monodentate ligands have been designed. The new catalysts provide significantly higher levels of activity than observed with the previously reported Ru- or Mo-based complexes. Enantiomerically enriched chiral alkylidenes are generated through diastereoselective reactions involving achiral Mo-based bispyrrolides and enantiomerically pure silyl-protected binaphthols. Such chiral catalysts initiate the key enantioselective ring-closing metathesis step in the total synthesis of quebrachamine efficiently (1 mol % loading, 22 °C, 1 h, >98% conversion, 84% yield) and with high selectivity (98:2 er, 96% ee). PMID:19113867

  16. An efficient protocol for the synthesis of highly sensitive indole imines utilizing green chemistry: optimization of reaction conditions.

    PubMed

    Nisar, Bushra; Rubab, Syeda Laila; Raza, Abdul Rauf; Tariq, Sobia; Sultan, Ayesha; Tahir, Muhammad Nawaz

    2018-04-11

    Novel and highly sensitive indole-based imines have been synthesized. Their synthesis has been compared employing a variety of protocols. Ultimately, a convenient, economical and high yielding set of conditions employing green chemistry have been designed for their synthesis.

  17. Measurement of host-to-activator transfer efficiency in nano-crystalline Y{sub 2}O{sub 3}:Eu{sup 3+} under VUV excitation

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

    Waite, Christopher; Mann, Rusty; Diaz, Anthony L., E-mail: DiazA@cwu.edu

    2013-02-15

    We have conducted a systematic study of the excitation and reflectance spectra of nano-crystalline Y{sub 2}O{sub 3}:Eu prepared by combustion synthesis. Excitation through the host lattice becomes relatively more efficient as the firing temperature of the precursor is increased, while reflectance properties remain essentially unchanged. Using these data, host-to-activator transfer efficiencies were calculated for excitation at the band edge of Y{sub 2}O{sub 3}, and evaluated using a competition kinetics model. From this analysis we conclude that the relatively low luminous efficiency of these materials is due more to poor bulk crystallinity than to surface loss effects. - Graphical abstract: Themore » low luminous efficiency of nano-crystalline Y{sub 2}O{sub 3}:Eu{sup 3+} prepared by combustion synthesis is due to poor bulk crystallinity rather than surface loss effects. Highlights: Black-Right-Pointing-Pointer We report on the optical properties of Y{sub 2}O{sub 3}:Eu{sup 3+} prepared by combustion synthesis. Black-Right-Pointing-Pointer Host-to-activator transfer efficiencies under VUV excitation were calculated. Black-Right-Pointing-Pointer The low luminous efficiency of these materials is due to poor bulk crystallinity.« less

  18. Analysis of effect of flameholder characteristics on lean, premixed, partially vaporized fuel-air mixtures quality and nitrogen oxides emissions

    NASA Technical Reports Server (NTRS)

    Cooper, L. P.

    1981-01-01

    An analysis was conducted of the effect of flameholding devices on the precombustion fuel-air characteristics and on oxides of nitrogen (NOx) emissions for combustion of premixed partially vaporized mixtures. The analysis includes the interrelationships of flameholder droplet collection efficiency, reatomization efficiency and blockage, and the initial droplet size distribution and accounts for the contribution of droplet combustion in partially vaporized mixtures to NOx emissions. Application of the analytical procedures is illustrated and parametric predictions of NOx emissions are presented.

  19. Enhancement of the reduction efficiency of soluble starch for platinum nanoparticles synthesis.

    PubMed

    Tongsakul, Duangta; Wongravee, Kanet; Thammacharoen, Chuchaat; Ekgasit, Sanong

    2012-08-01

    In this work, the efficiency of soluble starch as a reducing and a stabilizing agent in the synthesis of platinum nanoparticles under acidic-alkaline treatment is systematically studied. The degraded intermediates with reducing potential (i.e., small molecules containing aldehyde and α-hydroxy ketone moieties) are concomitantly generated when the alkaline concentration is greater than 0.025 M. The in situ generated species could completely reduce platinum ions (20 mM) and sufficiently stabilize the obtained platinum nanoparticles (5 mM) of uniform particle size (2-4 nm). The reduction is efficient and rapid as a complete conversion is achieved within 5 min. In a stronger alkaline condition, the platinum nanoparticles tend to aggregate and form a bigger domain because extensive degradation generates small starch fragments with less stabilization efficiency. This observation suggests that starch is a promising green material which could be chemically treated and transformed to a powerful reducing agent and stabilizer for the synthesis of metal nanoparticles. Copyright © 2012 Elsevier Ltd. All rights reserved.

  20. Rapid and accurate synthesis of TALE genes from synthetic oligonucleotides.

    PubMed

    Wang, Fenghua; Zhang, Hefei; Gao, Jingxia; Chen, Fengjiao; Chen, Sijie; Zhang, Cuizhen; Peng, Gang

    2016-01-01

    Custom synthesis of transcription activator-like effector (TALE) genes has relied upon plasmid libraries of pre-fabricated TALE-repeat monomers or oligomers. Here we describe a novel synthesis method that directly incorporates annealed synthetic oligonucleotides into the TALE-repeat units. Our approach utilizes iterative sets of oligonucleotides and a translational frame check strategy to ensure the high efficiency and accuracy of TALE-gene synthesis. TALE arrays of more than 20 repeats can be constructed, and the majority of the synthesized constructs have perfect sequences. In addition, this novel oligonucleotide-based method can readily accommodate design changes to the TALE repeats. We demonstrated an increased gene targeting efficiency against a genomic site containing a potentially methylated cytosine by incorporating non-conventional repeat variable di-residue (RVD) sequences.

  1. Efficient assessment of modified nucleoside stability under conditions of automated oligonucleotide synthesis: characterization of the oxidation and oxidative desulfurization of 2-thiouridine.

    PubMed

    Sochacka, E

    2001-01-01

    In order to efficiently assess the chemical stability of modified nucleosides to the reagents and conditions of automated oligonucleotide synthesis, we designed, developed and tested a scheme in which the modified nucleoside, directly attached to a solid support, is exposed to the cyclic chemistry of the instrument. Stability of 2-thiouridine against different oxidizers was investigated. Tertbutyl hydroperoxide (1 M) in anhydrous acetonitrile was a more effective oxidizer for the incorporation of 2-thiouridine into oligonucleotide chains than the same oxidizer in methylene chloride. Carbon tetrachloride/water in the presence of a basic catalyst was superior in maintaining the thiocarbonyl function, but its utility for RNA synthesis has yet to be fully tested, whereas 2-phenylsulfonyloxaziridine was a very efficient reagent for oxidative desulfurization of 2-thiouridine.

  2. Design and efficient synthesis of novel GM2 analogues with respect to the elucidation of the function of GM2 activator.

    PubMed

    Komori, Tatsuya; Ando, Takayuki; Imamura, Akihiro; Li, Yu-Teh; Ishida, Hideharu; Kiso, Makoto

    2008-10-01

    To elucidate the mechanism underlying the hydrolysis of the GalNAcbeta1-->4Gal linkage in ganglioside GM2 [GalNAcbeta1-->4(NeuAcalpha2-->3)Galbeta1-->4Glcbeta1-->1' Cer] by beta-hexosaminidase A (Hex A) with GM2 activator protein, we designed and synthesized two kinds of GM2 linkage analogues-6'-NeuAc-GM2 and alpha-GalNAc-GM2. In this paper, the efficient and systematic synthesis of these GM2 analogues was described. The highlight of our synthesis process is that the key intermediates, newly developed sialyllactose derivatives, were efficiently prepared in sufficient quantities; these derivatives directly served as highly reactive glycosyl acceptors and coupled with GalNTroc donors to furnish the assembly of GM2 tetrasaccharides in large quantities.

  3. Approximation concepts for efficient structural synthesis

    NASA Technical Reports Server (NTRS)

    Schmit, L. A., Jr.; Miura, H.

    1976-01-01

    It is shown that efficient structural synthesis capabilities can be created by using approximation concepts to mesh finite element structural analysis methods with nonlinear mathematical programming techniques. The history of the application of mathematical programming techniques to structural design optimization problems is reviewed. Several rather general approximation concepts are described along with the technical foundations of the ACCESS 1 computer program, which implements several approximation concepts. A substantial collection of structural design problems involving truss and idealized wing structures is presented. It is concluded that since the basic ideas employed in creating the ACCESS 1 program are rather general, its successful development supports the contention that the introduction of approximation concepts will lead to the emergence of a new generation of practical and efficient, large scale, structural synthesis capabilities in which finite element analysis methods and mathematical programming algorithms will play a central role.

  4. Eco-efficient one-pot synthesis of quinazoline-2,4(1H,3H)-diones at room temperature in water.

    PubMed

    Tian, Xin-Chuan; Huang, Xing; Wang, Dan; Gao, Feng

    2014-01-01

    An efficient one-pot synthesis of quinazoline-2,4(1H,3H)-diones was developed. First, the reactions of anthranilic acid derivatives with potassium cyanate afforded the corresponding urea derivatives. Then, cyclization of the urea derivatives with NaOH afforded the monosodium salts of benzoylene urea. Finally, HCl treatment afforded the desired products in near-quantitative yields. This is an eco-efficient method because all the reactions were carried out in water, and the desired products were obtained simply by filtration. The aqueous filtrate was the only waste generated from the reaction. We scaled up the reaction to 1 kg starting material, thus establishing an alternative approach for the green synthesis of quinazoline-2,4(1H,3H)-diones in the chemical and pharmaceutical industries.

  5. Two-photon absorbing porphyrins for oxygen microscopy (Conference Presentation)

    NASA Astrophysics Data System (ADS)

    Esipova, Tatiana V.; Vinogradov, Sergei A.

    2016-03-01

    The ability to quantify oxygen in vivo in 3D with high spatial and temporal resolution is invaluable for many areas of the biomedical science, including ophthalmology, neuroscience, cancer and stem biology. An optical method based on oxygen-dependent quenching of phosphorescence is being developed, that allows quantitative minimally invasive real-time imaging of partial pressure of oxygen (pO2) in tissue. In the past, dendritically protected phosphorescent oxygen probes with controllable quenching parameters and defined bio-distributions have been developed. More recently our probe strategy has extended to encompass two-photon excitable oxygen probes, which brought about first demonstrations of two-photon phosphorescence lifetime microscopy (2PLM) of oxygen in vivo, providing new valuable information for neuroscience and stem cell biology. However, current two-photon oxygen probes suffer from a number of limitations, such as low brightness and high cost of synthesis, which dramatically reduce imaging performance and limit usability of the method. Here we present an approach to new bright phosphorescent chromophores with internally enhanced two-photon absorption cross-sections, which pave a way to novel proves for 2PLM. In addition to substantial increase in performance, the new probes can be synthesized by much more efficient methods, thereby greatly reducing the cost of the synthesis and making the technique accessible to a broader range of researchers across different fields.

  6. Cross-linked nanoassemblies from poly(ethylene glycol)-poly(aspartate) block copolymers as stable supramolecular templates for particulate drug delivery.

    PubMed

    Lee, Hyun Jin; Bae, Younsoo

    2011-07-11

    Block copolymer cross-linked nanoassemblies (CNAs) were developed as stable supramolecular templates for particulate drug delivery. Poly(ethylene glycol)-poly(aspartate) [PEG-p(Asp)] block copolymers, consisting of PEG (5 or 12 kDa) and Asp (5, 14, 25, 33, and 37 repeating units), were used as scaffolds and grafts in combination to prepare a nanoassembly library of grafted nanoassemblies (GNAs) and CNAs. Four synthesis routes were tested to maximize the number of drug-binding Asp units per nanoassembly. Grafting-onto-scaffold and grafting-from-scaffold methods were used for GNA synthesis. Either partially or completely deprotected PEG-p(Asp) was cross-linked with diamine compounds to prepare CNAs. (1)H NMR and GPC measurements showed that GNAs and CNAs contained the maximum 183 and 253 Asp units, respectively. Initial screening of the nanoassemblies revealed that GNAs would be impractical for further development as drug carriers due to variable grafting efficiency and low product yields. CNAs were obtained in high yields and identified as a promising supramolecular template that can entrap and release ionizable drugs (doxorubicin), enhancing the particle stability of nanoassemblies in the pharmaceutically relevant pH ranges between 4 and 9. Light scattering measurements demonstrated that the particle size of CNAs remained uniform before and after drug entrapment, causing neither aggregation nor dissociation (<5 mg/mL).

  7. Application of a chitosan-immobilized Talaromyces thermophilus lipase to a batch biodiesel production from waste frying oils.

    PubMed

    Romdhane, Ines Belhaj-Ben; Romdhane, Zamen Ben; Bouzid, Maha; Gargouri, Ali; Belghith, Hafedh

    2013-12-01

    Waste frying oil, which not only harms people's health but also causes environmental pollution, can be a good alternative to partially substitute petroleum diesel through transesterification reaction. This oil contained 8.8 % of free fatty acids, which cause a problem in a base-catalyzed process. In this study, synthesis of biodiesel was efficiently catalyzed by the covalently immobilized Talaromyces thermophilus lipase and allowed bioconversion yield up to 92 % after 24 h of reaction time. The optimal molar ratio was four to six parts of methanol to one part of oil with a biocatalyst loaded of 25 wt.% of oil. Further, experiments revealed that T. thermophilus lipase, immobilized by a multipoint covalent liaison onto activated chitosan via a short spacer (glutaraldehyde), was sufficiently tolerant to methanol. In fact, using the stepwise addition of methanol, no significant difference was observed from the one-step whole addition at the start of reaction. The batch biodiesel synthesis was performed in a fixed bed reactor with a lipase loaded of 10 g. The bioconversion yield of 98 % was attained after a 5-h reaction time. The bioreactor was operated successfully for almost 150 h without any changes in the initial conversion yield. Most of the chemical and physical properties of the produced biodiesel meet the European and USA standard specifications of biodiesel fuels.

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

    Xia, Shuangluo; Vashishtha, Ashwani; Bulkley, David

    During DNA synthesis, base stacking and Watson-Crick (WC) hydrogen bonding increase the stability of nascent base pairs when they are in a ternary complex. To evaluate the contribution of base stacking to the incorporation efficiency of dNTPs when a DNA polymerase encounters an abasic site, we varied the penultimate base pairs (PBs) adjacent to the abasic site using all 16 possible combinations. We then determined pre-steady-state kinetic parameters with an RB69 DNA polymerase variant and solved nine structures of the corresponding ternary complexes. The efficiency of incorporation for incoming dNTPs opposite an abasic site varied between 2- and 210-fold dependingmore » on the identity of the PB. We propose that the A rule can be extended to encompass the fact that DNA polymerase can bypass dA/abasic sites more efficiently than other dN/abasic sites. Crystal structures of the ternary complexes show that the surface of the incoming base was stacked against the PB's interface and that the kinetic parameters for dNMP incorporation were consistent with specific features of base stacking, such as surface area and partial charge-charge interactions between the incoming base and the PB. Without a templating nucleotide residue, an incoming dNTP has no base with which it can hydrogen bond and cannot be desolvated, so that these surrounding water molecules become ordered and remain on the PB's surface in the ternary complex. When these water molecules are on top of a hydrophobic patch on the PB, they destabilize the ternary complex, and the incorporation efficiency of incoming dNTPs is reduced.« less

  9. Synthesis and biological evaluation of radio and dye labeled amino functionalized dendritic polyglycerol sulfates as multivalent anti-inflammatory compounds.

    PubMed

    Gröger, Dominic; Paulus, Florian; Licha, Kai; Welker, Pia; Weinhart, Marie; Holzhausen, Cornelia; Mundhenk, Lars; Gruber, Achim D; Abram, Ulrich; Haag, Rainer

    2013-09-18

    Herein we describe a platform technology for the synthesis and characterization of partially aminated, (35)S-labeled, dendritic polyglycerol sulfate (dPG(35)S amine) and fluorescent dPGS indocarbocyanine (ICC) dye conjugates. These polymer conjugates, based on a biocompatible dendritic polyglycerol scaffold, exhibit a high affinity to inflamed tissue in vivo and represent promising candidates for therapeutic and diagnostic applications. By utilizing a one-step sequential copolymerization approach, dendritic polyglycerol (Mn ≈ 4.5 kDa) containing 9.4% N-phthalimide protected amine functionalities was prepared on a large scale. Sulfation and simultaneous radio labeling with (35)SO3 pyridine complex, followed by cleavage of the N-phthalimide protecting groups, yielded dPG(35)S amine as a beta emitting, inflammation specific probe with free amino functionalities for conjugation. Furthermore, efficient labeling procedures with ICC via iminothiolane modification and subsequent "Michael" addition of the maleimide functionalized ICC dye, as well as by amide formation via NHS derivatized ICC on a dPGS amine scaffold, are described. The dPGS-ICC conjugates were investigated with respect to their photophysical properties, and both the radiolabeled and fluorescent compounds were comparatively visualized in histological tissue sections (radio detection and fluorescence microscopy) of animals treated with dPGS. Furthermore, cellular uptake of dPGS-ICC was found in endothelial cord blood (HUVEC) and the epithelial lung cells (A549). The presented synthetic routes allow a reproducible, controlled synthesis of dPGS amine on kilogram scale applying a one-pot batch reaction process. dPGS amine can be used for analysis via radioactivity or fluorescence, thereby creating a new platform for inflammation specific, multimodal imaging purposes using other attachable probes or contrast agents.

  10. Sulfur partitioning between glutathione and protein synthesis determines plant growth.

    PubMed

    Speiser, Anna; Silbermann, Marleen; Dong, Yihan; Haberland, Stefan; Uslu, Veli Vural; Wang, Shanshan; Bangash, Sajid A K; Reichelt, Michael; Meyer, Andreas J; Wirtz, Markus; Hell, Ruediger

    2018-05-11

    Photoautotrophic organisms must efficiently allocate their resources between stress-response pathways and growth-promoting pathways to be successful in a constantly changing environment. In this study, we addressed the coordination of sulfur flux between biosynthesis of the reactive oxygen species scavenger glutathione (GSH) and protein translation as one example of a central resource allocation switch. We crossed the Arabidopsis (Arabidopsis thaliana) GSH synthesis depleted cadmium-sensitive cad2-1 mutant, which lacks glutamate Cys ligase, into the sulfite reductase (SiR) sir1-1 mutant, which suffers from a significantly decreased flux of sulfur into cysteine and is consequently retarded in growth. Surprisingly, depletion of GSH synthesis promoted the growth of the sir1-1 cad2-1 double mutant (s1c2) when compared to sir1-1. Determination of GSH levels and in vivo live-cell imaging of the reduction-oxidation sensitive green fluorescent protein (roGFP2)-sensor demonstrated significant oxidation of the plastidic GSH redox-potential in cad2-1 and s1c2. This oxidized GSH redox-potential aligned with significant activation of plastid-localized sulfate reduction and a significantly higher flux of sulfur into proteins. The specific activation of the serine/threonine sensor kinase Target Of Rapamycin (TOR) in cad2-1 and s1c2 was the trigger for reallocation of cysteine from GSH biosynthesis into protein translation. Activation of TOR in s1c2 enhanced ribosome abundance and partially rescued the decreased meristematic activity observed in sir1-1 mutants. Therefore, we found that the coordination of sulfur flux between glutathione biosynthesis and protein translation determines growth via regulation of TOR. {copyright, serif} 2018 American Society of Plant Biologists. All rights reserved.

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

    Setyopratomo, P., E-mail: puguh-sptm@yahoo.com; Wulan, Praswasti P. D. K., E-mail: wulanmakmur@gmail.com; Sudibandriyo, M., E-mail: msudib@che.ui.ac.id

    Carbon nanotubes were produced by chemical vapor deposition method to meet the specifications for hydrogen storage. So far, the various catalyst had been studied outlining their activities, performances, and efficiencies. In this work, tri-metallic catalyst consist of Fe-Co-Mo supported on MgO was used. The catalyst was prepared by wet-impregnation method. Liquefied Petroleum Gas (LPG) was used as carbon source. The synthesis was conducted in atmospheric fixed bed reactor at reaction temperature range 750 – 850 °C for 30 minutes. The impregnation method applied in this study successfully deposed metal component on the MgO support surface. It found that the depositedmore » metal components might partially replace Mg(OH){sub 2} or MgO molecules in their crystal lattice. Compare to the original MgO powder; it was significant increases in pore volume and surface area has occurred during catalyst preparation stages. The size of obtained carbon nanotubes is ranging from about 10.83 nm OD/4.09 nm ID up to 21.84 nm OD/6.51 nm ID, which means that multiwall carbon nanotubes were formed during the synthesis. Yield as much as 2.35 g.CNT/g.catalyst was obtained during 30 minutes synthesis and correspond to carbon nanotubes growth rate of 0.2 μm/min. The BET surface area of the obtained carbon nanotubes is 181.13 m{sup 2}/g and around 50 % of which is contributed by mesopores. Micropore with half pore width less than 1 nm contribute about 10% volume of total micro and mesopores volume of the carbon nanotubes. The existence of these micropores is very important to increase the hydrogen storage capacity of the carbon nanotubes.« less

  12. Activation of IFN-beta element by IRF-1 requires a posttranslational event in addition to IRF-1 synthesis.

    PubMed Central

    Watanabe, N; Sakakibara, J; Hovanessian, A G; Taniguchi, T; Fujita, T

    1991-01-01

    Expression of the Type I IFN (i.e., IFN-alpha s and IFN-beta) genes is efficiently induced by viruses at the transcriptional level. This induction is mediated by at least two types of positive regulatory elements located in the human IFN-beta gene promoter: (1) the repeated elements which bind both the transcriptional activator IRF-1 and the repressor IRF-2 (IRF-elements; IRF-Es), and (2) the kappa B element (kappa B-E), which binds NF kappa B and is located between the IRF-Es and the TATA box. In this study we demonstrate that a promoter containing synthetic IRF-E, which displays high affinity for the IRFs can be efficiently activated by Newcastle disease virus (NDV). In contrast, such activation was either very weak or nil when cells were treated by IFN-beta or tumor necrosis factor-alpha (TNF-alpha), despite the fact they both efficiently induce de novo synthesis of the short-lived IRF-1 in L929 cells. In fact, efficient activation of the IRF-E apparently requires an event in addition to de novo IRF-1 induction, which can be elicited by NDV even in the presence of protein synthesis inhibitor, cycloheximide. Moreover, efficient activation of the IRF-E by NDV is specifically inhibited by the protein kinase inhibitor, Staurosporin. Hence our results suggest the importance of IRF-1 synthesis and post-translational modification event(s), possibly phosphorylation for the efficient activation of IRF-Es, which are otherwise under negative regulation by IRF-2. Images PMID:1886766

  13. The thermodynamic efficiency of ATP synthesis in oxidative phosphorylation.

    PubMed

    Nath, Sunil

    2016-12-01

    As the chief energy source of eukaryotic cells, it is important to determine the thermodynamic efficiency of ATP synthesis in oxidative phosphorylation (OX PHOS). Previous estimates of the thermodynamic efficiency of this vital process have ranged from Lehninger's original back-of-the-envelope calculation of 38% to the often quoted value of 55-60% in current textbooks of biochemistry, to high values of 90% from recent information theoretic considerations, and reports of realizations of close to ideal 100% efficiencies by single molecule experiments. Hence this problem has been reinvestigated from first principles. The overall thermodynamic efficiency of ATP synthesis in the mitochondrial energy transduction OX PHOS process has been found to lie between 40 and 41% from four different approaches based on a) estimation using structural and biochemical data, b) fundamental nonequilibrium thermodynamic analysis, c) novel insights arising from Nath's torsional mechanism of energy transduction and ATP synthesis, and d) the overall balance of cellular energetics. The torsional mechanism also offers an explanation for the observation of a thermodynamic efficiency approaching 100% in some experiments. Applications of the unique, molecular machine mode of functioning of F 1 F O -ATP synthase involving direct inter-conversion of chemical and mechanical energies in the design and fabrication of novel, man-made mechanochemical devices have been envisaged, and some new ways to exorcise Maxwell's demon have been proposed. It is hoped that analysis of the fundamental problem of energy transduction in OX PHOS from a fresh perspective will catalyze new avenues of research in this interdisciplinary field. Copyright © 2016 Elsevier B.V. All rights reserved.

  14. Rapid Size- Controlled Synthesis of Dextran-Coated, Copper-Doped Iron Oxide Nanoparticles

    NASA Astrophysics Data System (ADS)

    Wong, Ray M.

    2011-12-01

    Development of dual modality probes enabled for magnetic resonance imaging (MRI) and positron emission tomography (PET) has been on the rise in recent years due to the potential for these probes to facilitate combining the complementary high resolution of MRI and the high sensitivity of PET. The efficient synthesis of multimodal probes that include the radiolabels for PET can be hindered due to prolonged reaction times during radioisotope incorporation, and the resulting decay of the radiolabel. Along with a time-efficient synthesis, one also needs an optimal synthesis that yields products in a desirable size range (between 20-100 nm) to increase blood retention time. In this work, we describe a novel, rapid, microwave-based synthesis of dextran-coated iron oxide nanoparticles doped with copper (DIO/Cu). Traditional methods for synthesizing dextran-coated iron oxide particles require refluxing for 2 hours and result in approximately 50 nm particles. We demonstrate that microwave synthesis can produce 50 nm nanoparticles in 5 minutes of heating. We discuss the various parameters used in the microwave synthesis protocol to vary the size distribution of DIO/Cu, and demonstrate the successful incorporation of copper into these particles with the aim of future use for rapid 64Cu incorporation.

  15. Efficient synthesis of dichlorodenafil, an unapproved sildenafil analogue appearing in non-prescription supplements.

    PubMed

    Kim, Jong Yup; Hwang, In Gyun; Oh, Jae Ho; Kang, Il Hyun; Kwon, Sung Won; Kim, Deukjoon

    2013-01-01

    We have developed an efficient synthesis of dichlorodenafil (4), an unapproved sildenafil analogue isolated from dietary supplements. Our sequence employs POCl(3)-mediated chlorination of readily available chloroacetyl compound 7 followed by selective hydrolysis of the chloro-heterocycle function. Our synthesis confirms the structure of the illegal additive, and will provide regulatory agencies with ready access to authentic standard samples of dichlorodenafil (4) to aid in their mission to protect the public from unapproved and potentially harmful erectile dysfunction (ED) drug analogues that are added to herbal and dietary supplements without providing users with appropriate toxicological or pharmacological information.

  16. Synthesis of Ureas from CO2.

    PubMed

    Wang, Hua; Xin, Zhuo; Li, Yuehui

    2017-04-01

    Ureas are an important class of bioactive organic compounds in organic chemistry and exist widely in natural products, agricultural pesticides, uron herbicides, pharmaceuticals. Even though urea itself has been synthesized from CO 2 and ammonia for a long time, the selective and efficient synthesis of substituted ureas is still challenging due to the difficulty of dehydration processes. Efficient and economic fixation of CO 2 is of great importance in solving the problems of resource shortages, environmental issues, global warming, etc. During recent decades, chemists have developed different catalytic systems to synthesize ureas from CO 2 and amines. Herein, we focus on catalytic synthesis of ureas using CO 2 and amines.

  17. Facile Synthesis of Monodisperse Gold Nanocrystals Using Virola oleifera

    NASA Astrophysics Data System (ADS)

    Milaneze, Bárbara A.; Oliveira, Jairo P.; Augusto, Ingrid; Keijok, Wanderson J.; Côrrea, Andressa S.; Ferreira, Débora M.; Nunes, Otalíbio C.; Gonçalves, Rita de Cássia R.; Kitagawa, Rodrigo R.; Celante, Vinícius G.; da Silva, André Romero; Pereira, Ana Claudia H.; Endringer, Denise C.; Schuenck, Ricardo P.; Guimarães, Marco C. C.

    2016-10-01

    The development of new routes and strategies for nanotechnology applications that only employ green synthesis has inspired investigators to devise natural systems. Among these systems, the synthesis of gold nanoparticles using plant extracts has been actively developed as an alternative, efficient, cost-effective, and environmentally safe method for producing nanoparticles, and this approach is also suitable for large-scale synthesis. This study reports reproducible and completely natural gold nanocrystals that were synthesized using Virola oleifera extract. V. oleifera resin is rich in epicatechin, ferulic acid, gallic acid, and flavonoids (i.e., quercetin and eriodictyol). These gold nanoparticles play three roles. First, these nanoparticles exhibit remarkable stability based on their zeta potential. Second, these nanoparticles are functionalized with flavonoids, and third, an efficient, economical, and environmentally friendly mechanism can be employed to produce green nanoparticles with organic compounds on the surface. Our model is capable of reducing the resin of V. oleifera, which creates stability and opens a new avenue for biological applications. This method does not require painstaking conditions or hazardous agents and is a rapid, efficient, and green approach for the fabrication of monodisperse gold nanoparticles.

  18. Magnetic Heat Pump Containing Flow Diverters

    NASA Technical Reports Server (NTRS)

    Howard, Frank S.

    1995-01-01

    Proposed magnetic heat pump contains flow diverters for suppression of undesired flows. If left unchecked, undesired flows mix substantial amounts of partially heated and partially cooled portions of working fluid, effectively causing leakage of heat from heated side to cooled side. By reducing leakage of heat, flow diverters increase energy efficiency of magnetic heat pump, potentially offering efficiency greater than compressor-driven refrigerator.

  19. Amylopectin-g-poly(methylacrylate-co-sodium acrylate): An efficient Cd(II) binder.

    PubMed

    Sasmal, Dinabandhu; Kolya, Haradhan; Tripathy, Tridib

    2016-10-01

    Synthesis, characterization and Cd(II) adsorption studies of a novel biodegradable graft copolymer based on partially hydrolysed polymethylacrylate (PMA) grafted amylopectin was reported, which was prepared by first grafting of PMA chains onto the amylopectin backbone followed by partial alkaline hydrolysis. The hydrolysed graft copolymer (PHAP) was characterized by measuring saponification equivalent (SE), FTIR, (1)H NMR and (13)C NMR spectroscopy and thermal analysis (TG/DTG). The graft copolymer was biodegradable. Various operating variables affecting the metal sorption such as, amount of adsorbent, solution pH, contact time, temperature and Cd(II) solution concentration were studied which showed that the maximum adsorption of Cd(II) was found at pH 5.5, temperature 90°C, time 120min, polymer dose, 0.02g/L and initial Cd(II) concentration, 50mg/L. The adsorption data were well described by the pseudo-second-order and Langmuir isotherm model. Metal complexation studies were carried out experimentally using UV-visible, FTIR spectroscopy and theoretically using Density Functional Theory by Gaussian 09 and Gauss view 5.0 programmes which confirms a square planer geometry involving Cd(II) and COO(-) groups. Calculation of the various thermodynamic parameters was also done. The negative value of free energy change indicates the spontaneous nature of the adsorption. Copyright © 2016 Elsevier B.V. All rights reserved.

  20. S-Adenosylmethionine metabolism and its relation to polyamine synthesis in rat liver. Effect of nutritional state, adrenal function, some drugs and partial hepatectomy

    PubMed Central

    Eloranta, Terho O.; Raina, Aarne M.

    1977-01-01

    S-Adenosylmethionine metabolism and its relation to the synthesis and accumulation of polyamines was studied in rat liver under various nutritional conditions, in adrenalectomized or partially hepatectomized animals and after treatment with cortisol, thioacetamide or methylglyoxal bis(guanylhydrazone) {1,1′-[(methylethanediylidine)dinitrilo]diguanidine}. Starvation for 2 days only slightly affected S-adenosylmethionine metabolism. The ratio of spermidine/spermine decreased markedly, but the concentration of total polyamines did not change significantly. The activity of S-adenosylmethionine decarboxylase initially decreased and then increased during prolonged starvation. This increase was dependent on intact adrenals. Re-feeding of starved animals caused a rapid but transient stimulation of polyamine synthesis and also increased the concentrations of S-adenosylmethionine and S-adenosylhomocysteine. Similarly, cortisol treatment enhanced the synthesis of polyamines, S-adenosylmethionine and S-adenosylhomocysteine. Feeding with a methionine-deficient diet for 7–14 days profoundly increased the concentration of spermidine, whereas the concentrations of total polyamines and of S-adenosylmethionine showed no significant changes. The results show that nutritional state and adrenal function play a significant role in the regulation of hepatic metabolism of S-adenosylmethionine and polyamines. They further indicate that under a variety of physiological and experimental conditions the concentrations of S-adenosylmethionine and of total polyamines remain fairly constant and that changes in polyamine metabolism are not primarily connected with changes in the accumulation of S-adenosylmethionine or S-adenosylhomocysteine. PMID:597268

  1. Parallelizing quantum circuit synthesis

    NASA Astrophysics Data System (ADS)

    Di Matteo, Olivia; Mosca, Michele

    2016-03-01

    Quantum circuit synthesis is the process in which an arbitrary unitary operation is decomposed into a sequence of gates from a universal set, typically one which a quantum computer can implement both efficiently and fault-tolerantly. As physical implementations of quantum computers improve, the need is growing for tools that can effectively synthesize components of the circuits and algorithms they will run. Existing algorithms for exact, multi-qubit circuit synthesis scale exponentially in the number of qubits and circuit depth, leaving synthesis intractable for circuits on more than a handful of qubits. Even modest improvements in circuit synthesis procedures may lead to significant advances, pushing forward the boundaries of not only the size of solvable circuit synthesis problems, but also in what can be realized physically as a result of having more efficient circuits. We present a method for quantum circuit synthesis using deterministic walks. Also termed pseudorandom walks, these are walks in which once a starting point is chosen, its path is completely determined. We apply our method to construct a parallel framework for circuit synthesis, and implement one such version performing optimal T-count synthesis over the Clifford+T gate set. We use our software to present examples where parallelization offers a significant speedup on the runtime, as well as directly confirm that the 4-qubit 1-bit full adder has optimal T-count 7 and T-depth 3.

  2. Partially Turboelectric Aircraft Drive Key Performance Parameters

    NASA Technical Reports Server (NTRS)

    Jansen, Ralph H.; Duffy, Kirsten P.; Brown, Gerald V.

    2017-01-01

    The purpose of this paper is to propose electric drive specific power, electric drive efficiency, and electrical propulsion fraction as the key performance parameters for a partially turboelectric aircraft power system and to investigate their impact on the overall aircraft performance. Breguet range equations for a base conventional turbofan aircraft and a partially turboelectric aircraft are found. The benefits and costs that may result from the partially turboelectric system are enumerated. A break even analysis is conducted to find the minimum allowable electric drive specific power and efficiency, for a given electrical propulsion fraction, that can preserve the range, fuel weight, operating empty weight, and payload weight of the conventional aircraft. Current and future power system performance is compared to the required performance to determine the potential benefit.

  3. Neuroendocrine factors affecting the glycogen metabolism of purified Mytilus edulis glycogen cells: partial characterization of the putative glycogen mobilization hormone--demonstration of a factor that stimulates glycogen synthesis.

    PubMed

    Robbins, I; Lenoir, F; Mathieu, M

    1991-04-01

    A putative glycogen mobilizing hormone (GMH) from the marine mussel Mytilus edulis L. has been partially characterized. GMH activity is present in the cerebral ganglia and the hemolymph serum and promotes the mobilization of glycogen in isolated glycogen cells. The cerebral GMH is trypsin sensitive and partially heat labile and has an apparent molecular mass of greater than 20 kDa. Following fractionation of cerebral extracts by molecular mass, a second factor, with a molecular mass of ca. 1.5 kDa, was discovered. This factor stimulates post-incubation incorporation of 14C into glycogen in isolated glycogen cells.

  4. A monolithic and flexible fluoropolymer film microreactor for organic synthesis applications.

    PubMed

    Kim, Jin-Oh; Kim, Heejin; Ko, Dong-Hyeon; Min, Kyoung-Ik; Im, Do Jin; Park, Soo-Young; Kim, Dong-Pyo

    2014-11-07

    A photocurable and viscous fluoropolymer with chemical stability is a highly desirable material for fabrication of microchemical devices. Lack of a reliable fabrication method, however, limits actual applications for organic reactions. Herein, we report fabrication of a monolithic and flexible fluoropolymer film microreactor and its use as a new microfluidic platform. The fabrication involves facile soft lithography techniques that enable partial curing of thin laminates, which can be readily bonded by conformal contact without any external forces. We demonstrate fabrication of various functional channels (~300 μm thick) such as those embedded with either a herringbone micromixer pattern or a droplet generator. Organic reactions under strongly acidic and basic conditions can be carried out in this film microreactor even at elevated temperature with excellent reproducibility. In particular, the transparent film microreactor with good deformability could be wrapped around a light-emitting lamp for close contact with the light source for efficient photochemical reactions with visible light, which demonstrates easy integration with optical components for functional miniaturized systems.

  5. Platinum single-atom and cluster catalysis of the hydrogen evolution reaction

    NASA Astrophysics Data System (ADS)

    Cheng, Niancai; Stambula, Samantha; Wang, Da; Banis, Mohammad Norouzi; Liu, Jian; Riese, Adam; Xiao, Biwei; Li, Ruying; Sham, Tsun-Kong; Liu, Li-Min; Botton, Gianluigi A.; Sun, Xueliang

    2016-11-01

    Platinum-based catalysts have been considered the most effective electrocatalysts for the hydrogen evolution reaction in water splitting. However, platinum utilization in these electrocatalysts is extremely low, as the active sites are only located on the surface of the catalyst particles. Downsizing catalyst nanoparticles to single atoms is highly desirable to maximize their efficiency by utilizing nearly all platinum atoms. Here we report on a practical synthesis method to produce isolated single platinum atoms and clusters using the atomic layer deposition technique. The single platinum atom catalysts are investigated for the hydrogen evolution reaction, where they exhibit significantly enhanced catalytic activity (up to 37 times) and high stability in comparison with the state-of-the-art commercial platinum/carbon catalysts. The X-ray absorption fine structure and density functional theory analyses indicate that the partially unoccupied density of states of the platinum atoms' 5d orbitals on the nitrogen-doped graphene are responsible for the excellent performance.

  6. The KASE approach to domain-specific software systems

    NASA Technical Reports Server (NTRS)

    Bhansali, Sanjay; Nii, H. Penny

    1992-01-01

    Designing software systems, like all design activities, is a knowledge-intensive task. Several studies have found that the predominant cause of failures among system designers is lack of knowledge: knowledge about the application domain, knowledge about design schemes, knowledge about design processes, etc. The goal of domain-specific software design systems is to explicitly represent knowledge relevant to a class of applications and use it to partially or completely automate various aspects of the designing systems within that domain. The hope is that this would reduce the intellectual burden on the human designers and lead to more efficient software development. In this paper, we present a domain-specific system built on top of KASE, a knowledge-assisted software engineering environment being developed at the Stanford Knowledge Systems Laboratory. We introduce the main ideas underlying the construction of domain specific systems within KASE, illustrate the application of the idea in the synthesis of a system for tracking aircraft from radar signals, and discuss some of the issues in constructing domain-specific systems.

  7. Platinum single-atom and cluster catalysis of the hydrogen evolution reaction

    PubMed Central

    Cheng, Niancai; Stambula, Samantha; Wang, Da; Banis, Mohammad Norouzi; Liu, Jian; Riese, Adam; Xiao, Biwei; Li, Ruying; Sham, Tsun-Kong; Liu, Li-Min; Botton, Gianluigi A.; Sun, Xueliang

    2016-01-01

    Platinum-based catalysts have been considered the most effective electrocatalysts for the hydrogen evolution reaction in water splitting. However, platinum utilization in these electrocatalysts is extremely low, as the active sites are only located on the surface of the catalyst particles. Downsizing catalyst nanoparticles to single atoms is highly desirable to maximize their efficiency by utilizing nearly all platinum atoms. Here we report on a practical synthesis method to produce isolated single platinum atoms and clusters using the atomic layer deposition technique. The single platinum atom catalysts are investigated for the hydrogen evolution reaction, where they exhibit significantly enhanced catalytic activity (up to 37 times) and high stability in comparison with the state-of-the-art commercial platinum/carbon catalysts. The X-ray absorption fine structure and density functional theory analyses indicate that the partially unoccupied density of states of the platinum atoms' 5d orbitals on the nitrogen-doped graphene are responsible for the excellent performance. PMID:27901129

  8. Back scattering involving embedded silicon nitride (SiN) nanoparticles for c-Si solar cells

    NASA Astrophysics Data System (ADS)

    Ghosh, Hemanta; Mitra, Suchismita; Siddiqui, M. S.; Saxena, A. K.; Chaudhuri, Partha; Saha, Hiranmay; Banerjee, Chandan

    2018-04-01

    A novel material, structure and method of synthesis for dielectric light trapping have been presented in this paper. First, the light scattering behaviour of silicon nitride nanoparticles have been theoretically studied in order to find the optimized size for dielectric back scattering by FDTD simulations from Lumerical Inc. The optical results have been used in electrical analysis and thereby, estimate the effect of nanoparticles on efficiency of the solar cells depending on substrate thickness. Experimentally, silicon nitride (SiN) nanoparticles have been formed using hydrogen plasma treatment on SiN layer deposited by Plasma Enhanced Chemical Vapour Deposition (PECVD). The size and area coverage of the nanoparticles were controlled by varying the working pressure, power density and treatment duration. The nanoparticles were integrated with partial rear contact c-Si solar cells as dielectric back reflector structures for the light trapping in thin silicon solar cells. Experimental results revealed the increases of current density by 2.7% in presence of SiN nanoparticles.

  9. Synthesis of molybdenum carbide superconducting compounds by microwave-plasma chemical vapor deposition

    NASA Astrophysics Data System (ADS)

    Zhao, Hongyang; Cai, Kang; Ma, Zhibin; Cheng, Zhenxiang; Jia, Tingting; Kimura, Hideo; Fu, Qiuming; Tao, Hong; Xiong, Liwei

    2018-02-01

    A method to synthesize molybdenum carbides has been developed based on microwave plasma treatment with methane and hydrogen mixed gases, using a microwave-plasma chemical vapor deposition device. The device framework and its mechanism are described in detail. Two-dimensional α-Mo2C has been directly synthesized by a plate-to-plate substrate holder structure with a microwave power of 920 W and a partial pressure of 20 kPa. In-situ optical emission spectroscopy was used to measure the radical types in the plasma ball during glow discharge. The as-grown α-Mo2C samples were characterized by X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy and Raman spectroscopy to determine their phases, purity and chemical groups. The superconducting transition temperature was measured, and the transition temperatures of the relevant phases are discussed in detail. The results confirmed that this method is an efficient way to obtain molybdenum carbides and inspire new research interest in transition metal carbides, which have many intrinsic local properties and applications.

  10. Cleavage of beta,beta-carotene to flavor compounds by fungi.

    PubMed

    Zorn, H; Langhoff, S; Scheibner, M; Berger, R G

    2003-09-01

    More than 50 filamentous fungi and yeasts, known for de novo synthesis or biotransformation of mono-, sesqui-, tri-, or tetraterpenes, were screened for their ability to cleave beta,beta-carotene to flavor compounds. Ten strains discolored a beta,beta-carotene-containing growth agar, indicating efficient degradation of beta,beta-carotene. Dihydroactinidiolide was formed as the sole conversion product of beta,beta-carotene in submerged cultures of Ganoderma applanatum, Hypomyces odoratus, Kuehneromyces mutabilis, and Trametes suaveolens. When mycelium-free culture supernatants from five species were applied for the conversions, nearly complete degradation of beta,beta-carotene was observed after 12 h. Carotenoid-derived volatile products were detected in the media of Ischnoderma benzoinum, Marasmius scorodonius, and Trametes versicolor. beta-Ionone proved to be the main metabolite in each case, whereas beta-cyclocitral, dihydroactinidiolide, and 2-hydroxy-2,6,6-trimethylcyclohexanone were formed in minor quantities. Using a photometric bleaching test, the beta,beta-carotene cleaving enzyme activities of M. scorodonius were partially characterized.

  11. Toolboxes for a standardised and systematic study of glycans

    PubMed Central

    2014-01-01

    Background Recent progress in method development for characterising the branched structures of complex carbohydrates has now enabled higher throughput technology. Automation of structure analysis then calls for software development since adding meaning to large data collections in reasonable time requires corresponding bioinformatics methods and tools. Current glycobioinformatics resources do cover information on the structure and function of glycans, their interaction with proteins or their enzymatic synthesis. However, this information is partial, scattered and often difficult to find to for non-glycobiologists. Methods Following our diagnosis of the causes of the slow development of glycobioinformatics, we review the "objective" difficulties encountered in defining adequate formats for representing complex entities and developing efficient analysis software. Results Various solutions already implemented and strategies defined to bridge glycobiology with different fields and integrate the heterogeneous glyco-related information are presented. Conclusions Despite the initial stage of our integrative efforts, this paper highlights the rapid expansion of glycomics, the validity of existing resources and the bright future of glycobioinformatics. PMID:24564482

  12. An Easy-to-Machine Electrochemical Flow Microreactor: Efficient Synthesis of Isoindolinone and Flow Functionalization.

    PubMed

    Folgueiras-Amador, Ana A; Philipps, Kai; Guilbaud, Sébastien; Poelakker, Jarno; Wirth, Thomas

    2017-11-27

    Flow electrochemistry is an efficient methodology to generate radical intermediates. An electrochemical flow microreactor has been designed and manufactured to improve the efficiency of electrochemical flow reactions. With this device only little or no supporting electrolytes are needed, making processes less costly and enabling easier purification. This is demonstrated by the facile synthesis of amidyl radicals used in intramolecular hydroaminations to produce isoindolinones. The combination with inline mass spectrometry facilitates a much easier combination of chemical steps in a single flow process. © 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

  13. Chemoselective synthesis of ketones and ketimines by addition of organometallic reagents to secondary amides

    NASA Astrophysics Data System (ADS)

    Bechara, William S.; Pelletier, Guillaume; Charette, André B.

    2012-03-01

    The development of efficient and selective transformations is crucial in synthetic chemistry as it opens new possibilities in the total synthesis of complex molecules. Applying such reactions to the synthesis of ketones is of great importance, as this motif serves as a synthetic handle for the elaboration of numerous organic functionalities. In this context, we report a general and chemoselective method based on an activation/addition sequence on secondary amides allowing the controlled isolation of structurally diverse ketones and ketimines. The generation of a highly electrophilic imidoyl triflate intermediate was found to be pivotal in the observed exceptional functional group tolerance, allowing the facile addition of readily available Grignard and diorganozinc reagents to amides, and avoiding commonly observed over-addition or reduction side reactions. The methodology has been applied to the formal synthesis of analogues of the antineoplastic agent Bexarotene and to the rapid and efficient synthesis of unsymmetrical diketones in a one-pot procedure.

  14. Influence of Oxygen Partial Pressure during Processing on the Thermoelectric Properties of Aerosol-Deposited CuFeO₂.

    PubMed

    Stöcker, Thomas; Exner, Jörg; Schubert, Michael; Streibl, Maximilian; Moos, Ralf

    2016-03-24

    In the field of thermoelectric energy conversion, oxide materials show promising potential due to their good stability in oxidizing environments. Hence, the influence of oxygen partial pressure during synthesis on the thermoelectric properties of Cu-Delafossites at high temperatures was investigated in this study. For these purposes, CuFeO₂ powders were synthetized using a conventional mixed-oxide technique. X-ray diffraction (XRD) studies were conducted to determine the crystal structures of the delafossites associated with the oxygen content during the synthesis. Out of these powders, films with a thickness of about 25 µm were prepared by the relatively new aerosol-deposition (AD) coating technique. It is based on a room temperature impact consolidation process (RTIC) to deposit dense solid films of ceramic materials on various substrates without using a high-temperature step during the coating process. On these dense CuFeO₂ films deposited on alumina substrates with electrode structures, the Seebeck coefficient and the electrical conductivity were measured as a function of temperature and oxygen partial pressure. We compared the thermoelectric properties of both standard processed and aerosol deposited CuFeO₂ up to 900 °C and investigated the influence of oxygen partial pressure on the electrical conductivity, on the Seebeck coefficient and on the high temperature stability of CuFeO₂. These studies may not only help to improve the thermoelectric material in the high-temperature case, but may also serve as an initial basis to establish a defect chemical model.

  15. Selective antibacterial effects of mixed ZnMgO nanoparticles

    NASA Astrophysics Data System (ADS)

    Vidic, Jasmina; Stankic, Slavica; Haque, Francia; Ciric, Danica; Le Goffic, Ronan; Vidy, Aurore; Jupille, Jacques; Delmas, Bernard

    2013-05-01

    Antibiotic resistance has impelled the research for new agents that can inhibit bacterial growth without showing cytotoxic effects on humans and other species. We describe the synthesis and physicochemical characterization of nanostructured ZnMgO whose antibacterial activity was compared to its pure nano-ZnO and nano-MgO counterparts. Among the three oxides, ZnO nanocrystals—with the length of tetrapod legs about 100 nm and the diameter about 10 nm—were found to be the most effective antibacterial agents since both Gram-positive ( B. subtilis) and Gram-negative ( E. coli) bacteria were completely eradicated at concentration of 1 mg/mL. MgO nanocubes (the mean cube size 50 nm) only partially inhibited bacterial growth, whereas ZnMgO nanoparticles (sizes corresponding to pure particles) revealed high specific antibacterial activity to Gram-positive bacteria at this concentration. Transmission electron microscopy analysis showed that B. subtilis cells were damaged after contact with nano-ZnMgO, causing cell contents to leak out. Our preliminary toxicological study pointed out that nano-ZnO is toxic when applied to human HeLa cells, while nano-MgO and the mixed oxide did not induce any cell damage. Overall, our results suggested that nanostructured ZnMgO, may reconcile efficient antibacterial efficiency while being a safe new therapeutic for bacterial infections.

  16. Asymmetric Synthesis of Apratoxin E.

    PubMed

    Mao, Zhuo-Ya; Si, Chang-Mei; Liu, Yi-Wen; Dong, Han-Qing; Wei, Bang-Guo; Lin, Guo-Qiang

    2016-10-21

    An efficient method for asymmetric synthesis of apratoxin E 2 is described in this report. The chiral lactone 8, recycled from the degradation of saponin glycosides, was utilized to prepare the non-peptide fragment 6. In addition to this "from nature to nature" strategy, olefin cross-metathesis (CM) was applied as an alternative approach for the formation of the double bond. Moreover, pentafluorophenyl diphenylphosphinate was found to be an efficient condensation reagent for the macrocyclization.

  17. Chemoenzymatic convergent synthesis of 2'-O,4'-C-methyleneribonucleosides.

    PubMed

    Sharma, Vivek K; Kumar, Manish; Olsen, Carl E; Prasad, Ashok K

    2014-07-03

    Novozyme-435-catalyzed efficient regioselective acetylation of one of the two diastereotopic hydroxymethyl functions in 3-O-benzyl-4-C-hydroxymethyl-1,2-O-isopropylidene-α-d-ribofuranose has been achieved. The enzymatic methodology has been successfully utilized for convergent synthesis of bicyclic nucleosides (LNA monomers) T, U, A, and C. Further, it has been demonstrated that Novozyme-435 can be used for 10 cycles of the acylation reaction without losing selectivity and efficiency.

  18. [Pd(μ-Cl)Cl(IPr*)]2: a highly hindered pre-catalyst for the synthesis of tetra-ortho-substituted biaryls via Grignard reagent cross-coupling.

    PubMed

    Lesieur, Mathieu; Slawin, Alexandra M Z; Cazin, Catherine S J

    2014-08-14

    The new well-defined catalyst [Pd(μ-Cl)Cl(IPr*)]2 enables the efficient Grignard reagent cross-coupling for the synthesis of tetra-ortho-substituted biaryls. The high reactivity of the complex is associated with the important bulkiness of the IPr* ligand. The dimer represents the most efficient catalyst reported to date for this challenging transformation.

  19. Enantioselective syntheses of lignin models: an efficient synthesis of B-O-4 dimers and trimers by using the Evans chiral auxiliary

    Treesearch

    Costyl N. Njiojob; Joseph J. Bozell; Brian K. Long; Thomas Elder; Rebecca E. Key; William T. Hartwig

    2016-01-01

    We describe an efficient five-step, enantioselective synthesis of (R,R)- and (S,S)-lignin dimer models possessing a B-O-4 linkage, by using the Evans chiral aldol reaction as a key step. Mitsunobu inversion of the (R,R)- or (S,S)-isomers generates the corresponding (R,S)- and (S,R)-diastereomers. We further extend this approach to the...

  20. Time- and energy-efficient solution combustion synthesis of binary metal tungstate nanoparticles with enhanced photocatalytic activity.

    PubMed

    Thomas, Abegayl; Janáky, Csaba; Samu, Gergely F; Huda, Muhammad N; Sarker, Pranab; Liu, J Ping; van Nguyen, Vuong; Wang, Evelyn H; Schug, Kevin A; Rajeshwar, Krishnan

    2015-05-22

    In the search for stable and efficient photocatalysts beyond TiO2 , the tungsten-based oxide semiconductors silver tungstate (Ag2 WO4 ), copper tungstate (CuWO4 ), and zinc tungstate (ZnWO4 ) were prepared using solution combustion synthesis (SCS). The tungsten precursor's influence on the product was of particular relevance to this study, and the most significant effects are highlighted. Each sample's photocatalytic activity towards methyl orange degradation was studied and benchmarked against their respective commercial oxide sample obtained by solid-state ceramic synthesis. Based on the results herein, we conclude that SCS is a time- and energy-efficient method to synthesize crystalline binary tungstate nanomaterials even without additional excessive heat treatment. As many of these photocatalysts possess excellent photocatalytic activity, the discussed synthetic strategy may open sustainable materials chemistry avenues to solar energy conversion and environmental remediation. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Efficiency, error and yield in light-directed maskless synthesis of DNA microarrays

    PubMed Central

    2011-01-01

    Background Light-directed in situ synthesis of DNA microarrays using computer-controlled projection from a digital micromirror device--maskless array synthesis (MAS)--has proved to be successful at both commercial and laboratory scales. The chemical synthetic cycle in MAS is quite similar to that of conventional solid-phase synthesis of oligonucleotides, but the complexity of microarrays and unique synthesis kinetics on the glass substrate require a careful tuning of parameters and unique modifications to the synthesis cycle to obtain optimal deprotection and phosphoramidite coupling. In addition, unintended deprotection due to scattering and diffraction introduce insertion errors that contribute significantly to the overall error rate. Results Stepwise phosphoramidite coupling yields have been greatly improved and are now comparable to those obtained in solid phase synthesis of oligonucleotides. Extended chemical exposure in the synthesis of complex, long oligonucleotide arrays result in lower--but still high--final average yields which approach 99%. The new synthesis chemistry includes elimination of the standard oxidation until the final step, and improved coupling and light deprotection. Coupling Insertions due to stray light are the limiting factor in sequence quality for oligonucleotide synthesis for gene assembly. Diffraction and local flare are by far the largest contributors to loss of optical contrast. Conclusions Maskless array synthesis is an efficient and versatile method for synthesizing high density arrays of long oligonucleotides for hybridization- and other molecular binding-based experiments. For applications requiring high sequence purity, such as gene assembly, diffraction and flare remain significant obstacles, but can be significantly reduced with straightforward experimental strategies. PMID:22152062

  2. Synthesis of modified proanthocyanidins: easy and general introduction of a hydroxy group at C-6 of catechin; efficient synthesis of elephantorrhizol.

    PubMed

    Boyer, François-Didier; Es-Safi, Nour-Eddine; Beauhaire, Josiane; Guernevé, Christine Le; Ducrot, Paul-Henri

    2005-02-01

    A general procedure for the oxidation of catechin derivatives is described, leading to the introduction of a new hydroxy group at C-6. This procedure has been applied for the synthesis of elephantorrhizol, a natural flavan-3-ol exhibiting a fully substituted cycle A.

  3. Witting Reaction Using a Stabilized Phosphorus Ylid: An Efficient and Stereoselective Synthesis of Ethyl Trans-Cinnamate

    ERIC Educational Resources Information Center

    Speed, Traci J.; Mclntyre, Jean P.; Thamattoor, Dasan M.

    2004-01-01

    An instructive experiment for the synthesis of ethyl trans-cinnamate, a pleasant smelling ester used in perfumery and flavoring by the reaction of benzaldehyde with the stable ylid triphenylphosphorane is described. The synthesis, workup and characterization of trans-cinnamate may be accomplished in a single laboratory session with commonly…

  4. Photochemical approaches to ordered polymers

    NASA Technical Reports Server (NTRS)

    Meador, Michael A.; Abdulaziz, Mahmoud; Meador, Mary Ann B.

    1990-01-01

    The photocyclization of o-benzyloxyphenyl ketone chromophores provides an efficient, high yield route to the synthesis of 2,3-diphenylbenzofurans. The synthesis and solution of photochemistry of a series of polymers containing this chromophore is described. The photocuring of these polymers is a potential new approach to the synthesis of highly conjugated polymers based upon a p-phenylene bisbenzofuran repeat unit.

  5. An efficient preparation of labelling precursor of [11C]L-deprenyl-D2 and automated radiosynthesis.

    PubMed

    Zirbesegger, Kevin; Buccino, Pablo; Kreimerman, Ingrid; Engler, Henry; Porcal, Williams; Savio, Eduardo

    2017-01-01

    The synthesis of [ 11 C]L-deprenyl-D 2 for imaging of astrocytosis with positron emission tomography (PET) in neurodegenerative diseases has been previously reported. [ 11 C]L-deprenyl-D 2 radiosynthesis requires a precursor, L-nordeprenyl-D 2 , which has been previously synthesized from L-amphetamine as starting material with low overall yields. Here, we present an efficient synthesis of L-nordeprenyl-D 2 organic precursor as free base and automated radiosynthesis of [ 11 C]L-deprenyl-D 2 for PET imaging of astrocytosis. The L-nordeprenyl-D 2 precursor was synthesized from the easily commercial available and cheap reagent L-phenylalanine in five steps. Next, N -alkylation of L-nordeprenyl-D 2 free base with [ 11 C]MeOTf was optimized using the automated commercial platform GE TRACERlab® FX C Pro. A simple and efficient synthesis of L-nordeprenyl-D 2 precursor of [ 11 C]L-deprenyl-D 2 as free base has been developed in five synthetic steps with an overall yield of 33%. The precursor as free base has been stable for 9 months stored at low temperature (-20 °C). The labelled product was obtained with 44 ± 13% ( n  = 12) (end of synthesis, decay corrected) radiochemical yield from [ 11 C]MeI after 35 min synthesis time. The radiochemical purity was over 99% in all cases and specific activity was (170 ± 116) GBq/μmol. A high-yield synthesis of [ 11 C]L-deprenyl-D 2 has been achieved with high purity and specific activity. L-nordeprenyl-D 2 precursor as free amine was applicable for automated production in a commercial synthesis module for preclinical and clinical application.

  6. High-yielding continuous-flow synthesis of antimalarial drug hydroxychloroquine

    PubMed Central

    Telang, Nakul S; Kong, Caleb J; Verghese, Jenson; Gilliland III, Stanley E; Ahmad, Saeed; Dominey, Raymond N

    2018-01-01

    Numerous synthetic methods for the continuous preparation of fine chemicals and active pharmaceutical ingredients (API’s) have been reported in recent years resulting in a dramatic improvement in process efficiencies. Herein we report a highly efficient continuous synthesis of the antimalarial drug hydroxychloroquine (HCQ). Key improvements in the new process include the elimination of protecting groups with an overall yield improvement of 52% over the current commercial process. The continuous process employs a combination of packed bed reactors with continuous stirred tank reactors for the direct conversion of the starting materials to the product. This high-yielding, multigram-scale continuous synthesis provides an opportunity to achieve increase global access to hydroxychloroquine for treatment of malaria. PMID:29623120

  7. Efficient synthesis of silver nanoparticles from Prosopis juliflora leaf extract and its antimicrobial activity using sewage

    NASA Astrophysics Data System (ADS)

    Raja, K.; Saravanakumar, A.; Vijayakumar, R.

    2012-11-01

    In this paper, aqueous extract of fresh leaves of Prosopis juliflora was used for the synthesis of silver (Ag) nanoparticles. UV-Vis spectroscopy studies were carried out to asses silver nanoparticles formation within 5 min, scanning electron microscopic was used to characterize shape of the Ag nanoparticles, X-ray diffraction analysis confirms the nanoparticles as crystalline silver and facecentered cubic type and Fourier transform infra-red assed that shows biomolecule compounds which are responsible for reduction and capping material of silver nanoparticles. The anti microbial activity of silver nanoparticle was performed using sewage. The approach of plant-mediated synthesis appears to be cost efficient, eco-friendly and easy methods.

  8. BETA: Behavioral testability analyzer and its application to high-level test generation and synthesis for testability. Ph.D. Thesis

    NASA Technical Reports Server (NTRS)

    Chen, Chung-Hsing

    1992-01-01

    In this thesis, a behavioral-level testability analysis approach is presented. This approach is based on analyzing the circuit behavioral description (similar to a C program) to estimate its testability by identifying controllable and observable circuit nodes. This information can be used by a test generator to gain better access to internal circuit nodes and to reduce its search space. The results of the testability analyzer can also be used to select test points or partial scan flip-flops in the early design phase. Based on selection criteria, a novel Synthesis for Testability approach call Test Statement Insertion (TSI) is proposed, which modifies the circuit behavioral description directly. Test Statement Insertion can also be used to modify circuit structural description to improve its testability. As a result, Synthesis for Testability methodology can be combined with an existing behavioral synthesis tool to produce more testable circuits.

  9. Indomethacin inhibits the effects of oestrogen in the anterior pituitary gland of the rat.

    PubMed

    Rosental, D G; Machiavelli, G A; Cherñavsky, A C; Speziale, N S; Burdman, J A

    1989-06-01

    Two inhibitors of prostaglandin synthesis, indomethacin and aspirin, blocked the increase of oestrogen-binding sites in the nuclear subcellular fraction, an increase which occurs after the administration of oestradiol. Consequently the biological effects of oestrogens in the anterior pituitary gland of the rat (prolactin synthesis, concentration of progesterone-binding sites and cell proliferation) are diminished. The anterior pituitary gland synthesized prostaglandin F2 alpha (PGF2 alpha), PGE2 and PGD2 from arachidonic acid. This synthesis was blocked when indomethacin was added to the culture media. Oestrogen increased the concentration of PGE2: an increase that was partially prevented by indomethacin. Prostaglandins may have an important role on the effects of oestrogen in the anterior pituitary gland of the rat.

  10. Highly efficient molybdenum-based catalysts for enantioselective alkene metathesis

    PubMed Central

    Malcolmson, Steven J.; Meek, Simon J.; Sattely, Elizabeth S.; Schrock, Richard R.; Hoveyda, Amir H.

    2009-01-01

    Discovery of efficient catalysts is one of the most compelling objectives of modern chemistry. Chiral catalysts are in particularly high demand, as they facilitate synthesis of enantiomerically enriched small molecules that are critical to developments in medicine, biology and materials science1. Especially noteworthy are catalysts that promote—with otherwise inaccessible efficiency and selectivity levels—reactions demonstrated to be of great utility in chemical synthesis. Here we report a class of chiral catalysts that initiate alkene metathesis1 with very high efficiency and enantioselectivity. Such attributes arise from structural fluxionality of the chiral catalysts and the central role that enhanced electronic factors have in the catalytic cycle. The new catalysts have a stereogenic metal centre and carry only monodentate ligands; the molybdenum-based complexes are prepared stereoselectively by a ligand exchange process involving an enantiomerically pure aryloxide, a class of ligands scarcely used in enantioselective catalysis2,3. We demonstrate the application of the new catalysts in an enantioselective synthesis of the Aspidosperma alkaloid, quebrachamine, through an alkene metathesis reaction that cannot be promoted by any of the previously reported chiral catalysts. PMID:19011612

  11. Effect of methane partial pressure on the performance of a membrane biofilm reactor coupling methane-dependent denitrification and anammox.

    PubMed

    Cai, Chen; Hu, Shihu; Chen, Xueming; Ni, Bing-Jie; Pu, Jiaoyang; Yuan, Zhiguo

    2018-10-15

    Complete nitrogen removal has recently been demonstrated by integrating anaerobic ammonium oxidation (anammox) and denitrifying anaerobic methane oxidation (DAMO) processes. In this work, the effect of methane partial pressure on the performance of a membrane biofilm reactor (MBfR) consisting of DAMO and anammox microorganisms was evaluated. The activities of DAMO archaea and DAMO bacteria in the biofilm increased significantly with increased methane partial pressure, from 367 ± 9 and 58 ± 22 mg-N L -1 d -1 to 580 ± 12 and 222 ± 22 mg-N L -1 d -1 , respectively, while the activity of anammox bacteria only increased slightly, when the methane partial pressure was elevated from 0.24 to 1.39 atm in the short-term batch tests. The results were supported by a long-term (seven weeks) continuous test, when the methane partial pressure was dropped from 1.39 to 0.78 atm. The methane utilization efficiency was always above 96% during both short-term and long-term tests. Taken together, nitrogen removal rate (especially the nitrate reduction rate by DAMO archaea) and methane utilization efficiency could be maintained at high levels in a broad range of methane partial pressure (0.24-1.39 atm in this study). In addition, a previously established DAMO/anammox biofilm model was used to analyze the experimental data. The observed impacts of methane partial pressure on biofilm activity were well explained by the modeling results. These results suggest that methane partial pressure can potentially be used as a manipulated variable to control reaction rates, ultimately to maintain high nitrogen removal efficiency, according to nitrogen loading rate. Copyright © 2018 Elsevier B.V. All rights reserved.

  12. An Eco-Friendly Improved Protocol for the Synthesis of Bis(3-indolyl)methanes Using Poly(4-vinylpyridinium)hydrogen Sulfate as Efficient, Heterogeneous, and Recyclable Solid Acid Catalyst

    PubMed Central

    Banothu, Janardhan; Gali, Rajitha; Velpula, Ravibabu; Bavantula, Rajitha; Crooks, Peter A.

    2013-01-01

    Highly efficient and eco-friendly protocol for the synthesis of bis(3-indolyl)methanes by the electrophilic substitution reaction of indole with aldehydes catalyzed by poly(4-vinylpyridinium)hydrogen sulfate was described. Excellent yields, shorter reaction times, simple work-up procedure, avoiding hazardous organic solvents, and reusability of the catalyst are the most obvious advantages of this method. PMID:24052864

  13. Reaction of cytidine nucleotides with cyanoacetylene: support for the intermediacy of nucleoside-2',3'-cyclic phosphates in the prebiotic synthesis of RNA.

    PubMed

    Crowe, Michael A; Sutherland, John D

    2006-06-01

    A robust and prebiotically plausible synthesis of RNA is a key requirement of the "RNA World" hypothesis, but, to date, no such synthesis has been demonstrated. Monomer synthesis strategies involving attachment of preformed nucleobases to sugars have failed, and, even if activated 5'-nucleotides could be made, the hydrolysis of these intermediates in water makes their efficient oligomerisation appear unlikely. We recently reported a synthesis of cytidine-2',3'-cyclic phosphate 1 (C>p) in which the nucleobase was assembled in stages on a sugar-phosphate template. However, 2',3'-cyclic nucleotides (N>p's) also undergo hydrolysis, in this case giving a mixture of the 2'- and 3'-monophosphates. This hydrolysis has previously been seen as making the, otherwise promising, oligomerisation of N>p's seem as unlikely as that of the 5'-activated nucleotides. We now find that cyanoacetylene, the reagent used for the second stage of nucleobase assembly in the synthesis of C>p, also reverses the effect of the hydrolysis by driving efficient cyclisation of C2'p and C3'p back to C>p. Excess cyanoacetylene also derivatises the nucleobase, but this modification is reversible at neutral pH. These findings significantly strengthen the case for N>p's in a prebiotic synthesis of RNA.

  14. Stereospecific synthesis of syn-α-oximinoamides by a three-component reaction of isocyanides, syn-chlorooximes, and carboxylic acids.

    PubMed

    Pirali, Tracey; Mossetti, Riccardo; Galli, Simona; Tron, Gian Cesare

    2011-07-15

    A stereospecific multicomponent reaction among isocyanides, syn-chlorooximes, and carboxylic acids provides an efficient synthesis of biologically relevant syn-α-oximinoamides. © 2011 American Chemical Society

  15. Investigation of innovative synthesis of biologically active compounds on the basis of newly developed reactions.

    PubMed

    Honda, Toshio

    2012-01-01

    Synthesis of biologically active compounds, including natural products and pharmaceutical agents, is an important and interesting research area since the large structural diversity and complexity of bioactive compounds make them an important source of leads and scaffolds in drug discovery and development. Many structurally and also biologically interesting compounds, including marine natural products, have been isolated from nature and have also been prepared on the basis of a computational design for the purpose of developing medicinal chemistry. In order to obtain a wide variety of derivatives of biologically active compounds from the viewpoint of medicinal chemistry, it is essential to establish efficient synthetic procedures for desired targets. Newly developed reactions should also be used for efficient synthesis of desired compounds. Thus, recent progress in the synthesis of biologically active compounds by focusing on the development of new reactions is summarized in this review article.

  16. Elucidating the reaction pathways in the synthesis of organolead trihalide perovskite for high-performance solar cells.

    PubMed

    Wang, Baohua; Young Wong, King; Xiao, Xudong; Chen, Tao

    2015-05-28

    The past two years have witnessed unprecedentedly rapid development of organic-inorganic halide perovskite-based solar cells. The solution-processability and high efficiency make this technology extraordinarily attractive. The intensive investigations have accumulated rich experiences in the perovskite fabrication; while the mechanism of the chemical synthesis still remains unresolved. Here, we set up the chemical equation of the synthesis and elucidate the reactions from both thermodynamic and kinetic perspectives. Our study shows that gaseous products thermodynamically favour the reaction, while the activation energy and "collision" probability synergistically determine the reaction rate. These understandings enable us to finely tune the crystal size for high-quality perovskite film, leading to a record fill factor among similar device structures in the literature. This investigation provides a general strategy to explore the mechanism of perovskite synthesis and benefits the fabrication of high-efficiency perovskite photoactive layer.

  17. Total synthesis of mycobacterial arabinogalactan containing 92 monosaccharide units

    NASA Astrophysics Data System (ADS)

    Wu, Yong; Xiong, De-Cai; Chen, Si-Cong; Wang, Yong-Shi; Ye, Xin-Shan

    2017-03-01

    Carbohydrates are diverse bio-macromolecules with highly complex structures that are involved in numerous biological processes. Well-defined carbohydrates obtained by chemical synthesis are essential to the understanding of their functions. However, synthesis of carbohydrates is greatly hampered by its insufficient efficiency. So far, assembly of long carbohydrate chains remains one of the most challenging tasks for synthetic chemists. Here we describe a highly efficient assembly of a 92-mer polysaccharide by the preactivation-based one-pot glycosylation protocol. Several linear and branched oligosaccharide/polysaccharide fragments ranging from 5-mer to 31-mer in length have been rapidly constructed in one-pot manner, which enables the first total synthesis of a biologically important mycobacterial arabinogalactan through a highly convergent [31+31+30] coupling reaction. Our results show that the preactivation-based one-pot glycosylation protocol may provide access to the construction of long and complicated carbohydrate chains.

  18. Local algebraic analysis of differential systems

    NASA Astrophysics Data System (ADS)

    Kaptsov, O. V.

    2015-06-01

    We propose a new approach for studying the compatibility of partial differential equations. This approach is a synthesis of the Riquier method, Gröbner basis theory, and elements of algebraic geometry. As applications, we consider systems including the wave equation and the sine-Gordon equation.

  19. Synthesis and Characterization of Partial Biobased Furan Polyamides

    DTIC Science & Technology

    2014-02-01

    Approved for public release; distribution is unlimited. NOTICES Disclaimers The...Weapons and Materials Research Directorate, ARL Approved for public release; distribution is unlimited...ii REPORT DOCUMENTATION PAGE Form Approved OMB No. 0704-0188 Public reporting burden for this collection of information is estimated to average

  20. High temperature desulfurization of synthesis gas

    DOEpatents

    Najjar, Mitri S.; Robin, Allen M.

    1989-01-01

    The hot process gas stream from the partial oxidation of sulfur-containing heavy liquid hydrocarbonaceous fuel and/or sulfur-containing solid carbonaceous fuel comprising gaseous mixtures of H.sub.2 +CO, sulfur-containing gases, entrained particulate carbon, and molten slag is passed through the unobstructed central passage of a radiant cooler where the temperature is reduced to a temperature in the range of about 1800.degree. F. to 1200.degree. F. From about 0 to 95 wt. % of the molten slag and/or entrained material may be removed from the hot process gas stream prior to the radiant cooler with substantially no reduction in temperature of the process gas stream. In the radiant cooler, after substantially all of the molten slag has solidified, the sulfur-containing gases are contacted with a calcium-containing material to produce calcium sulfide. A partially cooled stream of synthesis gas, reducing gas, or fuel gas containing entrained calcium sulfide particulate matter, particulate carbon, and solidified slag leaves the radiant cooler containing a greatly reduced amount of sulfur-containing gases.

  1. Enzymic synthesis of indole-3-acetyl-1-O-beta-d-glucose. I. Partial purification and characterization of the enzyme from Zea mays

    NASA Technical Reports Server (NTRS)

    Leznicki, A. J.; Bandurski, R. S.

    1988-01-01

    The first enzyme-catalyzed reaction leading from indole-3-acetic acid (IAA) to the myo-inositol esters of IAA is the synthesis of indole-3-acetyl-1-O-beta-D-glucose from uridine-5'-diphosphoglucose (UDPG) and IAA. The reaction is catalyzed by the enzyme, UDPG-indol-3-ylacetyl glucosyl transferase (IAA-glucose-synthase). This work reports methods for the assay of the enzyme and for the extraction and partial purification of the enzyme from kernels of Zea mays sweet corn. The enzyme has an apparent molecular weight of 46,500 an isoelectric point of 5.5, and its pH optimum lies between 7.3 and 7.6. The enzyme is stable to storage at zero degrees but loses activity during column chromatographic procedures which can be restored only fractionally by addition of column eluates. The data suggest either multiple unknown cofactors or conformational changes leading to activity loss.

  2. Plasma reforming and partial oxidation of hydrocarbon fuel vapor to produce synthesis gas and/or hydrogen gas

    DOEpatents

    Kong, Peter C.; Detering, Brent A.

    2003-08-19

    Methods and systems for treating vapors from fuels such as gasoline or diesel fuel in an internal combustion engine, to form hydrogen gas or synthesis gas, which can then be burned in the engine to produce more power. Fuel vapor, or a mixture of fuel vapor and exhaust gas and/or air, is contacted with a plasma, to promote reforming reactions between the fuel vapor and exhaust gas to produce carbon monoxide and hydrogen gas, partial oxidation reactions between the fuel vapor and air to produce carbon monoxide and hydrogen gas, or direct hydrogen and carbon particle production from the fuel vapor. The plasma can be a thermal plasma or a non-thermal plasma. The plasma can be produced in a plasma generating device which can be preheated by contact with at least a portion of the hot exhaust gas stream, thereby decreasing the power requirements of the plasma generating device.

  3. Plasma Reforming And Partial Oxidation Of Hydrocarbon Fuel Vapor To Produce Synthesis Gas And/Or Hydrogen Gas

    DOEpatents

    Kong, Peter C.; Detering, Brent A.

    2004-10-19

    Methods and systems are disclosed for treating vapors from fuels such as gasoline or diesel fuel in an internal combustion engine, to form hydrogen gas or synthesis gas, which can then be burned in the engine to produce more power. Fuel vapor, or a mixture of fuel vapor and exhaust gas and/or air, is contacted with a plasma, to promote reforming reactions between the fuel vapor and exhaust gas to produce carbon monoxide and hydrogen gas, partial oxidation reactions between the fuel vapor and air to produce carbon monoxide and hydrogen gas, or direct hydrogen and carbon particle production from the fuel vapor. The plasma can be a thermal plasma or a non-thermal plasma. The plasma can be produced in a plasma generating device which can be preheated by contact with at least a portion of the hot exhaust gas stream, thereby decreasing the power requirements of the plasma generating device.

  4. Synthesis and in Vitro and in Vivo Characterization of Highly β1-Selective β-Adrenoceptor Partial Agonists

    PubMed Central

    2013-01-01

    β-Adrenoceptor antagonists boast a 50-year use for symptomatic control in numerous cardiovascular diseases. One might expect highly selective antagonists are available for the human β-adrenoceptor subtype involved in these diseases, yet few truly β1-selective molecules exist. To address this clinical need, we re-evaluated LK 204-545 (1),1 a selective β1-adrenoceptor antagonist, and discovered it possessed significant partial agonism. Removal of 1’s aromatic nitrile afforded 19, a ligand with similar β1-adrenoceptor selectivity and partial agonism (log KD of −7.75 and −5.15 as an antagonist of functional β1- and β2-mediated responses, respectively, and 34% of the maximal response of isoprenaline (β1)). In vitro β-adrenoceptor selectivity and partial agonism of 19 were mirrored in vivo. We designed analogues of 19 to improve affinity, selectivity, and partial agonism. Although partial agonism could not be fully attenuated, SAR suggests that an extended alkoxyalkoxy side chain, alongside substituents at the meta- or para-positions of the phenylurea, increases ligand affinity and β1-selectivity. PMID:23614528

  5. Efficient synthesis of gamma-lactams by a tandem reductive amination/lactamization sequence.

    PubMed

    Nöth, Julica; Frankowski, Kevin J; Neuenswander, Benjamin; Aubé, Jeffrey; Reiser, Oliver

    2008-01-01

    A three-component method for the synthesis of highly substituted gamma-lactams from readily available maleimides, aldehydes, and amines is described. A new reductive amination/intramolecular lactamization sequence provides a straightforward route to the lactam products in a single manipulation. The general utility of this method is demonstrated by the parallel synthesis of a gamma-lactam library.

  6. Musical sound analysis/synthesis using vector-quantized time-varying spectra

    NASA Astrophysics Data System (ADS)

    Ehmann, Andreas F.; Beauchamp, James W.

    2002-11-01

    A fundamental goal of computer music sound synthesis is accurate, yet efficient resynthesis of musical sounds, with the possibility of extending the synthesis into new territories using control of perceptually intuitive parameters. A data clustering technique known as vector quantization (VQ) is used to extract a globally optimum set of representative spectra from phase vocoder analyses of instrument tones. This set of spectra, called a Codebook, is used for sinusoidal additive synthesis or, more efficiently, for wavetable synthesis. Instantaneous spectra are synthesized by first determining the Codebook indices corresponding to the best least-squares matches to the original time-varying spectrum. Spectral index versus time functions are then smoothed, and interpolation is employed to provide smooth transitions between Codebook spectra. Furthermore, spectral frames are pre-flattened and their slope, or tilt, extracted before clustering is applied. This allows spectral tilt, closely related to the perceptual parameter ''brightness,'' to be independently controlled during synthesis. The result is a highly compressed format consisting of the Codebook spectra and time-varying tilt, amplitude, and Codebook index parameters. This technique has been applied to a variety of harmonic musical instrument sounds with the resulting resynthesized tones providing good matches to the originals.

  7. A review on green synthesis of silver nanoparticles and their applications.

    PubMed

    Rafique, Muhammad; Sadaf, Iqra; Rafique, M Shahid; Tahir, M Bilal

    2017-11-01

    Development of reliable and eco-accommodating methods for the synthesis of nanoparticles is a vital step in the field of nanotechnology. Silver nanoparticles are important because of their exceptional chemical, physical, and biological properties, and hence applications. In the last decade, numerous efforts were made to develop green methods of synthesis to avoid the hazardous byproducts. This review describes the methods of green synthesis for Ag-NPs and their numerous applications. It also describes the comparison of efficient synthesis methods via green routes over physical and chemical methods, which provide strong evidence for the selection of suitable method for the synthesis of Ag-NPs.

  8. Quantum partial search for uneven distribution of multiple target items

    NASA Astrophysics Data System (ADS)

    Zhang, Kun; Korepin, Vladimir

    2018-06-01

    Quantum partial search algorithm is an approximate search. It aims to find a target block (which has the target items). It runs a little faster than full Grover search. In this paper, we consider quantum partial search algorithm for multiple target items unevenly distributed in a database (target blocks have different number of target items). The algorithm we describe can locate one of the target blocks. Efficiency of the algorithm is measured by number of queries to the oracle. We optimize the algorithm in order to improve efficiency. By perturbation method, we find that the algorithm runs the fastest when target items are evenly distributed in database.

  9. Improving maximum power point tracking of partially shaded photovoltaic system by using IPSO-BELBIC

    NASA Astrophysics Data System (ADS)

    Al-Alim El-Garhy, M. Abd; Mubarak, R. I.; El-Bably, M.

    2017-08-01

    Solar photovoltaic (PV) arrays in remote applications are often related to the rapid changes in the partial shading pattern. Rapid changes of the partial shading pattern make the tracking of maximum power point (MPP) of the global peak through the local ones too difficult. An essential need to make a fast and efficient algorithm to detect the peaks values which always vary as the sun irradiance changes. This paper presents two algorithms based on the improved particle swarm optimization technique one of them with PID controller (IPSO-PID), and the other one with Brain Emotional Learning Based Intelligent Controller (IPSO-BELBIC). These techniques improve the maximum power point (MPP) tracking capabilities for photovoltaic (PV) system under partial shading circumstances. The main aim of these improved algorithms is to accelerate the velocity of IPSO to reach to (MPP) and increase its efficiency. These algorithms also improve the tracking time under complex irradiance conditions. Based on these conditions, the tracking time of these presented techniques improves to 2 msec, with an efficiency of 100%.

  10. Nonenzymatic synthesis of RNA and DNA oligomers on hexitol nucleic acid templates: the importance of the A structure

    NASA Technical Reports Server (NTRS)

    Kozlov, I. A.; Politis, P. K.; Van Aerschot, A.; Busson, R.; Herdewijn, P.; Orgel, L. E.; Bada, J. L. (Principal Investigator); Dolan, M. (Principal Investigator)

    1999-01-01

    Hexitol nucleic acid (HNA) is an analogue of DNA containing the standard nucleoside bases, but with a phosphorylated 1,5-anhydrohexitol backbone. HNA oligomers form duplexes having the nucleic acid A structure with complementary DNA or RNA oligomers. The HNA decacytidylate oligomer is an efficient template for the oligomerization of the 5'-phosphoroimidazolides of guanosine or deoxyguanosine. Comparison of the oligomerization efficiencies on HNA, RNA, and DNA decacytidylate templates under various conditions suggests strongly that only nucleic acid double helices with the A structure support efficient template-directed synthesis when 5'-phosphoroimidazolides of nucleosides are used as substrates.

  11. Effects of exogenous fatty acids and inhibition of de novo fatty acid synthesis on disaturated phosphatidylcholine production by fetal lung cells and adult type II cells.

    PubMed

    Maniscalco, W M; Finkelstein, J N; Parkhurst, A B

    1989-05-01

    De novo fatty acid synthesis may be an important source of saturated fatty acids for fetal lung disaturated phosphatidylcholine (DSPC) production. To investigate the roles of de novo fatty acid synthesis and exogenous fatty acids, we incubated dispersed fetal lung cells and freshly isolated adult type II cells with exogenous palmitate and oleate and measured DSPC synthesis. Unlike adult type II cells, fetal lung cells did not increase DSPC synthesis when exogenous palmitate was available; adult type II cells increased DSPC synthesis by 70% in the presence of palmitate. Exogenous oleate decreased DSPC synthesis by 48% in fetal cells but not in adult type II cells. Incubation of fetal lung cells with TOFA [2-furancarboxylate, 5-(tetradecyloxy)-sodium], a metabolic inhibitor of fatty acid synthesis, decreased fatty acid synthesis by 65%. There was a simultaneous 56% inhibition of DSPC production, but no effect on protein, DNA, or glyceride-glycerol production, measured by precursor incorporation. The inhibition of DSPC synthesis associated with TOFA was partially prevented by exogenous palmitate but not oleate. Fetal cells prepared from explants that had been cultured in dexamethasone also had TOFA-associated inhibition of DSPC synthesis that was similar to non-dexamethasone-exposed cells. These studies suggest that under baseline conditions of low fatty acid availability, such as in the fetus, de novo fatty acid synthesis in fetal cells, but not in adult type II cells, provides sufficient saturated fatty acids to support maximal DSPC production. Inhibition of de novo fatty acid synthesis resulting in decreased DSPC production in fetal lung cells in conditions of low fatty acid availability suggests that fatty acid synthesis may be central to maintain DSPC synthesis in the fetus.

  12. The use of street-level bureaucracy theory in health policy analysis in low- and middle-income countries: a meta-ethnographic synthesis.

    PubMed

    Erasmus, Ermin

    2014-12-01

    This article presents a synthesis of studies that explicitly use the theory of street-level bureaucracy to illuminate health policy implementation in low- and middle-income countries. Street-level bureaucrats are frontline workers in bureaucracies, e.g. nurses, who regularly interact directly with citizens in discharging their policy implementation duties and who have some discretion over which services are offered, how services are offered and the benefits and sanctions allocated to citizens. This synthesis seeks to achieve the dual objectives of, first, reflecting on how street-level bureaucracy theory has been used in the literature and, second, providing an example of the application of the synthesis methodology of meta-ethnography to the health policy analysis literature. The article begins by outlining meta-ethnography and providing more information on the papers on which the synthesis is based. This is followed by a detailed account of how the synthesis was achieved and by an articulation of the synthesis. It then concludes with thoughts and questions on the value and relevance of the synthesis, the experience of conducting the synthesis and the partial way in which street-level bureaucracy theory has been used in the literature examined. Published by Oxford University Press in association with The London School of Hygiene and Tropical Medicine © The Author 2014; all rights reserved.

  13. Compound Synthesis or Growth and Development of Roots/Stomata Regulate Plant Drought Tolerance or Water Use Efficiency/Water Uptake Efficiency.

    PubMed

    Meng, Lai-Sheng

    2018-04-11

    Water is crucial to plant growth and development because it serves as a medium for all cellular functions. Thus, the improvement of plant drought tolerance or water use efficiency/water uptake efficiency is important in modern agriculture. In this review, we mainly focus on new genetic factors for ameliorating drought tolerance or water use efficiency/water uptake efficiency of plants and explore the involvement of these genetic factors in the regulation of improving plant drought tolerance or water use efficiency/water uptake efficiency, which is a result of altered stomata density and improving root systems (primary root length, hair root growth, and lateral root number) and enhanced production of osmotic protectants, which is caused by transcription factors, proteinases, and phosphatases and protein kinases. These results will help guide the synthesis of a model for predicting how the signals of genetic and environmental stress are integrated at a few genetic determinants to control the establishment of either water use efficiency or water uptake efficiency. Collectively, these insights into the molecular mechanism underpinning the control of plant drought tolerance or water use efficiency/water uptake efficiency may aid future breeding or design strategies to increase crop yield.

  14. Stereoselective synthesis of novel highly substituted isochromanone and isoquinolinone-containing exocyclic tetrasubstituted alkenes.

    PubMed

    Arthuis, Martin; Pontikis, Renée; Florent, Jean-Claude

    2009-03-06

    An efficient synthetic route toward the synthesis of highly substituted arylethylidene-isoquinolinones/isochromanones is reported. The tandem carbopalladation/Suzuki-Miyaura coupling sequence stereoselectively provided various functionalized polycyclic compounds in moderate to excellent yields.

  15. A facile and eco-friendly synthesis of diarylthiazoles and diarylimidazoles in water

    EPA Science Inventory

    A simple, efficient and high yielding greener protocol for the synthesis of substituted thiazoles and imidazoles is described that utilizes the reaction of readily available α-tosyloxy ketones with variety of thioamides/amidines in water

  16. Catalyst-Free Difunctionalization of Activated Alkenes in Water: Efficient Synthesis of β-Keto Sulfides and Sulfones.

    PubMed

    Wang, Huamin; Wang, Guangyu; Lu, Qingquan; Chiang, Chien-Wei; Peng, Pan; Zhou, Jiufu; Lei, Aiwen

    2016-10-04

    Difunctionalization of activated alkenes, a powerful strategy in chemical synthesis, has been accomplished for direct synthesis of a series of β-keto sulfides and β-keto sulfones. The transformation, mediated by O2 , proceeds smoothly in water and without any catalyst. Prominent advantages of this method include mild reaction conditions, purification simplicity, and gram-scale synthesis, underlining the practical utility of this methodology. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. An efficient synthesis strategy for metal-organic frameworks: Dry-gel synthesis of MOF-74 framework with high yield and improved performance

    DOE PAGES

    Das, Atanu Kumar; Vemuri, Rama Sesha; Kutnyakov, Igor; ...

    2016-06-16

    Here, vapor-assisted dry-gel synthesis of MOF-74 structure, specifically NiMOF-74 from its synthetic precursors, was conducted with high yield and improved performance showing promise for gas (CO 2) and water adsorption applications. Unlike conventional synthesis, which takes 72 h, this kinetic study showed that NiMOF-74 forms within 12 h under dry-gel conditions with similar performance characteristics and exhibits the best performance characteristics after 48 h of heating.

  18. Modal control theory and application to aircraft lateral handling qualities design

    NASA Technical Reports Server (NTRS)

    Srinathkumar, S.

    1978-01-01

    A multivariable synthesis procedure based on eigenvalue/eigenvector assignment is reviewed and is employed to develop a systematic design procedure to meet the lateral handling qualities design objectives of a fighter aircraft over a wide range of flight conditions. The closed loop modal characterization developed provides significant insight into the design process and plays a pivotal role in the synthesis of robust feedback systems. The simplicity of the synthesis algorithm yields an efficient computer aided interactive design tool for flight control system synthesis.

  19. Thermodynamic and achievable efficiencies for solar-driven electrochemical reduction of carbon dioxide to transportation fuels.

    PubMed

    Singh, Meenesh R; Clark, Ezra L; Bell, Alexis T

    2015-11-10

    Thermodynamic, achievable, and realistic efficiency limits of solar-driven electrochemical conversion of water and carbon dioxide to fuels are investigated as functions of light-absorber composition and configuration, and catalyst composition. The maximum thermodynamic efficiency at 1-sun illumination for adiabatic electrochemical synthesis of various solar fuels is in the range of 32-42%. Single-, double-, and triple-junction light absorbers are found to be optimal for electrochemical load ranges of 0-0.9 V, 0.9-1.95 V, and 1.95-3.5 V, respectively. Achievable solar-to-fuel (STF) efficiencies are determined using ideal double- and triple-junction light absorbers and the electrochemical load curves for CO2 reduction on silver and copper cathodes, and water oxidation kinetics over iridium oxide. The maximum achievable STF efficiencies for synthesis gas (H2 and CO) and Hythane (H2 and CH4) are 18.4% and 20.3%, respectively. Whereas the realistic STF efficiency of photoelectrochemical cells (PECs) can be as low as 0.8%, tandem PECs and photovoltaic (PV)-electrolyzers can operate at 7.2% under identical operating conditions. We show that the composition and energy content of solar fuels can also be adjusted by tuning the band-gaps of triple-junction light absorbers and/or the ratio of catalyst-to-PV area, and that the synthesis of liquid products and C2H4 have high profitability indices.

  20. Thermodynamic and achievable efficiencies for solar-driven electrochemical reduction of carbon dioxide to transportation fuels

    NASA Astrophysics Data System (ADS)

    Singh, Meenesh R.; Clark, Ezra L.; Bell, Alexis T.

    2015-11-01

    Thermodynamic, achievable, and realistic efficiency limits of solar-driven electrochemical conversion of water and carbon dioxide to fuels are investigated as functions of light-absorber composition and configuration, and catalyst composition. The maximum thermodynamic efficiency at 1-sun illumination for adiabatic electrochemical synthesis of various solar fuels is in the range of 32-42%. Single-, double-, and triple-junction light absorbers are found to be optimal for electrochemical load ranges of 0-0.9 V, 0.9-1.95 V, and 1.95-3.5 V, respectively. Achievable solar-to-fuel (STF) efficiencies are determined using ideal double- and triple-junction light absorbers and the electrochemical load curves for CO2 reduction on silver and copper cathodes, and water oxidation kinetics over iridium oxide. The maximum achievable STF efficiencies for synthesis gas (H2 and CO) and Hythane (H2 and CH4) are 18.4% and 20.3%, respectively. Whereas the realistic STF efficiency of photoelectrochemical cells (PECs) can be as low as 0.8%, tandem PECs and photovoltaic (PV)-electrolyzers can operate at 7.2% under identical operating conditions. We show that the composition and energy content of solar fuels can also be adjusted by tuning the band-gaps of triple-junction light absorbers and/or the ratio of catalyst-to-PV area, and that the synthesis of liquid products and C2H4 have high profitability indices.

  1. Chemoselective synthesis of functional homocysteine residues in polypeptides and peptides.

    PubMed

    Gharakhanian, Eric G; Deming, Timothy J

    2016-04-18

    A methodology was developed for efficient, chemoselective transformation of methionine residues into stable, functional homocysteine derivatives. Methionine residues can undergo highly chemoselective alkylation reactions at low pH to yield stable sulfonium ions, which could then be selectively demethylated to give stable alkyl homocysteine residues. This mild, two-step process is chemoselective, efficient, tolerates many functional groups, and provides a means for creation of new functional biopolymers, site-specific peptide tagging, and synthesis of biomimetic and structural analogs of peptides.

  2. Indirect synthesis of multi-degree of freedom transient systems. [linear programming for a kinematically linear system

    NASA Technical Reports Server (NTRS)

    Pilkey, W. D.; Chen, Y. H.

    1974-01-01

    An indirect synthesis method is used in the efficient optimal design of multi-degree of freedom, multi-design element, nonlinear, transient systems. A limiting performance analysis which requires linear programming for a kinematically linear system is presented. The system is selected using system identification methods such that the designed system responds as closely as possible to the limiting performance. The efficiency is a result of the method avoiding the repetitive systems analyses accompanying other numerical optimization methods.

  3. ACCESS 1: Approximation Concepts Code for Efficient Structural Synthesis program documentation and user's guide

    NASA Technical Reports Server (NTRS)

    Miura, H.; Schmit, L. A., Jr.

    1976-01-01

    The program documentation and user's guide for the ACCESS-1 computer program is presented. ACCESS-1 is a research oriented program which implements a collection of approximation concepts to achieve excellent efficiency in structural synthesis. The finite element method is used for structural analysis and general mathematical programming algorithms are applied in the design optimization procedure. Implementation of the computer program, preparation of input data and basic program structure are described, and three illustrative examples are given.

  4. Obstacles to Using Prior Research and Evaluations.

    ERIC Educational Resources Information Center

    Orwin, Robert G.

    1985-01-01

    The manner in which results and methods are reported influences the ability of the synthesis of prior studies for planning new evaluations. Confidence ratings, coding conventions, and supplemental evidence can partially overcome the difficulties. Planners must acknowledge the influence of their own judgement in using prior research. (Author)

  5. LIVER REGENERATION STUDIES WITH RAT HEPATOCYTES IN PRIMARY CULTURE

    EPA Science Inventory

    Adult rat parenchymal hepatocytes in primary culture can be induced to enter into DNA synthesis and mitosis. The optimal conditions for hepatocyte replication are low plating density (less than 10,000 cells/sq cm) and 50% serum from two-thirds partially hepatectomized rats (48 hr...

  6. Efficient automatic OCR word validation using word partial format derivation and language model

    NASA Astrophysics Data System (ADS)

    Chen, Siyuan; Misra, Dharitri; Thoma, George R.

    2010-01-01

    In this paper we present an OCR validation module, implemented for the System for Preservation of Electronic Resources (SPER) developed at the U.S. National Library of Medicine.1 The module detects and corrects suspicious words in the OCR output of scanned textual documents through a procedure of deriving partial formats for each suspicious word, retrieving candidate words by partial-match search from lexicons, and comparing the joint probabilities of N-gram and OCR edit transformation corresponding to the candidates. The partial format derivation, based on OCR error analysis, efficiently and accurately generates candidate words from lexicons represented by ternary search trees. In our test case comprising a historic medico-legal document collection, this OCR validation module yielded the correct words with 87% accuracy and reduced the overall OCR word errors by around 60%.

  7. Electride support boosts nitrogen dissociation over ruthenium catalyst and shifts the bottleneck in ammonia synthesis

    DOE PAGES

    Kitano, Masaaki; Kanbara, Shinji; Inoue, Yasunori; ...

    2015-03-30

    We actively sough novel approaches to efficient ammonia synthesis at an ambient pressure so as to reduce the cost of ammonia production and to allow for compact production facilities. It is accepted that the key is the development of a high-performance catalyst that significantly enhances dissociation of the nitrogen-nitrogen triple bond, which is generally considered a rate-determining step. Here we examine the kinetics of nitrogen and hydrogen isotope exchange and hydrogen adsorption/desorption reactions for a recently discovered efficient catalyst for ammonia synthesis --ruthenium-loaded 12CaO∙7AI 2O 3 electride (Ru/C12A7:more » $$\\bar{e}$$ )--and find that the rate controlling step of ammonia synthesis over Ru/C12A7:$$\\bar{e}$$ is not dissociation of the nitrogen-nitrogen triple bond but the subsequent formation of N-H n species. A mechanism of ammonia synthesis involving reversible storage and release of hydrogen atoms on the Ru/C12A7:$$\\bar{e}$$ surface is proposed on the basis of observed hydrogen adsorption/desorption kinetics.« less

  8. Electride support boosts nitrogen dissociation over ruthenium catalyst and shifts the bottleneck in ammonia synthesis

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

    Kitano, Masaaki; Kanbara, Shinji; Inoue, Yasunori

    We actively sough novel approaches to efficient ammonia synthesis at an ambient pressure so as to reduce the cost of ammonia production and to allow for compact production facilities. It is accepted that the key is the development of a high-performance catalyst that significantly enhances dissociation of the nitrogen-nitrogen triple bond, which is generally considered a rate-determining step. Here we examine the kinetics of nitrogen and hydrogen isotope exchange and hydrogen adsorption/desorption reactions for a recently discovered efficient catalyst for ammonia synthesis --ruthenium-loaded 12CaO∙7AI 2O 3 electride (Ru/C12A7:more » $$\\bar{e}$$ )--and find that the rate controlling step of ammonia synthesis over Ru/C12A7:$$\\bar{e}$$ is not dissociation of the nitrogen-nitrogen triple bond but the subsequent formation of N-H n species. A mechanism of ammonia synthesis involving reversible storage and release of hydrogen atoms on the Ru/C12A7:$$\\bar{e}$$ surface is proposed on the basis of observed hydrogen adsorption/desorption kinetics.« less

  9. Synthesis of the human insulin gene. Part III. Chemical synthesis of 5'-phosphomonoester group containing deoxyribooligonucleotides by the modified phosphotriester method. Its application in the synthesis of seventeen fragments constituting human insulin C-chain DNA.

    PubMed Central

    Hsiung, H M; Sung, W L; Brousseau, R; Wu, R; Narang, S A

    1980-01-01

    A method for phosphorylating a protected deoxyribooligonucleotide containing phosphotriester linkages is described. The modified phosphotriester method of chemical synthesis is further refined in terms of (i) better final deblocking conditions and (ii) new chromatography solvent systems containing acetone-water-ethyl acetate to yield pure oligomers. The effectiveness of these improvements has been demonstrated in the rapid and efficient synthesis of seventeen fragments constituting the sequence of human insulin C-chain DNA. Images PMID:7008029

  10. Rate in template-directed polymer synthesis.

    PubMed

    Saito, Takuya

    2014-06-01

    We discuss the temporal efficiency of template-directed polymer synthesis, such as DNA replication and transcription, under a given template string. To weigh the synthesis speed and accuracy on the same scale, we propose a template-directed synthesis (TDS) rate, which contains an expression analogous to that for the Shannon entropy. Increasing the synthesis speed accelerates the TDS rate, but the TDS rate is lowered if the produced sequences are diversified. We apply the TDS rate to some production system models and investigate how the balance between the speed and the accuracy is affected by changes in the system conditions.

  11. Efficient multiscale magnetic-domain analysis of iron-core material under mechanical stress

    NASA Astrophysics Data System (ADS)

    Nishikubo, Atsushi; Ito, Shumpei; Mifune, Takeshi; Matsuo, Tetsuji; Kaido, Chikara; Takahashi, Yasuhito; Fujiwara, Koji

    2018-05-01

    For an efficient analysis of magnetization, a partial-implicit solution method is improved using an assembled domain structure model with six-domain mesoscopic particles exhibiting pinning-type hysteresis. The quantitative analysis of non-oriented silicon steel succeeds in predicting the stress dependence of hysteresis loss with computation times greatly reduced by using the improved partial-implicit method. The effect of cell division along the thickness direction is also evaluated.

  12. Partial differential equations constrained combinatorial optimization on an adiabatic quantum computer

    NASA Astrophysics Data System (ADS)

    Chandra, Rishabh

    Partial differential equation-constrained combinatorial optimization (PDECCO) problems are a mixture of continuous and discrete optimization problems. PDECCO problems have discrete controls, but since the partial differential equations (PDE) are continuous, the optimization space is continuous as well. Such problems have several applications, such as gas/water network optimization, traffic optimization, micro-chip cooling optimization, etc. Currently, no efficient classical algorithm which guarantees a global minimum for PDECCO problems exists. A new mapping has been developed that transforms PDECCO problem, which only have linear PDEs as constraints, into quadratic unconstrained binary optimization (QUBO) problems that can be solved using an adiabatic quantum optimizer (AQO). The mapping is efficient, it scales polynomially with the size of the PDECCO problem, requires only one PDE solve to form the QUBO problem, and if the QUBO problem is solved correctly and efficiently on an AQO, guarantees a global optimal solution for the original PDECCO problem.

  13. Energy efficiency in nanoscale synthesis using nanosecond plasmas.

    PubMed

    Pai, David Z; Ken Ostrikov, Kostya; Kumar, Shailesh; Lacoste, Deanna A; Levchenko, Igor; Laux, Christophe O

    2013-01-01

    We report a nanoscale synthesis technique using nanosecond-duration plasma discharges. Voltage pulses 12.5 kV in amplitude and 40 ns in duration were applied repetitively at 30 kHz across molybdenum electrodes in open ambient air, generating a nanosecond spark discharge that synthesized well-defined MoO₃ nanoscale architectures (i.e. flakes, dots, walls, porous networks) upon polyamide and copper substrates. No nitrides were formed. The energy cost was as low as 75 eV per atom incorporated into a nanostructure, suggesting a dramatic reduction compared to other techniques using atmospheric pressure plasmas. These findings show that highly efficient synthesis at atmospheric pressure without catalysts or external substrate heating can be achieved in a simple fashion using nanosecond discharges.

  14. Efficient synthesis of silver nanoparticles from Prosopis juliflora leaf extract and its antimicrobial activity using sewage.

    PubMed

    Raja, K; Saravanakumar, A; Vijayakumar, R

    2012-11-01

    In this paper, aqueous extract of fresh leaves of Prosopis juliflora was used for the synthesis of silver (Ag) nanoparticles. UV-Vis spectroscopy studies were carried out to asses silver nanoparticles formation within 5 min, scanning electron microscopic was used to characterize shape of the Ag nanoparticles, X-ray diffraction analysis confirms the nanoparticles as crystalline silver and facecentered cubic type and Fourier transform infra-red assed that shows biomolecule compounds which are responsible for reduction and capping material of silver nanoparticles. The anti microbial activity of silver nanoparticle was performed using sewage. The approach of plant-mediated synthesis appears to be cost efficient, eco-friendly and easy methods. Copyright © 2012 Elsevier B.V. All rights reserved.

  15. Harnessing Thin-Film Continuous-Flow Assembly Lines.

    PubMed

    Britton, Joshua; Castle, Jared W; Weiss, Gregory A; Raston, Colin L

    2016-07-25

    Inspired by nature's ability to construct complex molecules through sequential synthetic transformations, an assembly line synthesis of α-aminophosphonates has been developed. In this approach, simple starting materials are continuously fed through a thin-film reactor where the intermediates accrue molecular complexity as they progress through the flow system. Flow chemistry allows rapid multistep transformations to occur via reaction compartmentalization, an approach not amenable to using conventional flasks. Thin film processing can also access facile in situ solvent exchange to drive reaction efficiency, and through this method, α-aminophosphonate synthesis requires only 443 s residence time to produce 3.22 g h(-1) . Assembly-line synthesis allows unprecedented reaction flexibility and processing efficiency. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Influence of Oxygen Partial Pressure during Processing on the Thermoelectric Properties of Aerosol-Deposited CuFeO2

    PubMed Central

    Stöcker, Thomas; Exner, Jörg; Schubert, Michael; Streibl, Maximilian; Moos, Ralf

    2016-01-01

    In the field of thermoelectric energy conversion, oxide materials show promising potential due to their good stability in oxidizing environments. Hence, the influence of oxygen partial pressure during synthesis on the thermoelectric properties of Cu-Delafossites at high temperatures was investigated in this study. For these purposes, CuFeO2 powders were synthetized using a conventional mixed-oxide technique. X-ray diffraction (XRD) studies were conducted to determine the crystal structures of the delafossites associated with the oxygen content during the synthesis. Out of these powders, films with a thickness of about 25 µm were prepared by the relatively new aerosol-deposition (AD) coating technique. It is based on a room temperature impact consolidation process (RTIC) to deposit dense solid films of ceramic materials on various substrates without using a high-temperature step during the coating process. On these dense CuFeO2 films deposited on alumina substrates with electrode structures, the Seebeck coefficient and the electrical conductivity were measured as a function of temperature and oxygen partial pressure. We compared the thermoelectric properties of both standard processed and aerosol deposited CuFeO2 up to 900 °C and investigated the influence of oxygen partial pressure on the electrical conductivity, on the Seebeck coefficient and on the high temperature stability of CuFeO2. These studies may not only help to improve the thermoelectric material in the high-temperature case, but may also serve as an initial basis to establish a defect chemical model. PMID:28773351

  17. Ceramic oxygen transport membrane array reactor and reforming method

    DOEpatents

    Kelly, Sean M.; Christie, Gervase Maxwell; Rosen, Lee J.; Robinson, Charles; Wilson, Jamie R.; Gonzalez, Javier E.; Doraswami, Uttam R.

    2016-09-27

    A commercially viable modular ceramic oxygen transport membrane reforming reactor for producing a synthesis gas that improves the thermal coupling of reactively-driven oxygen transport membrane tubes and catalyst reforming tubes required to efficiently and effectively produce synthesis gas.

  18. Enantioselective synthesis of spirooxoindoles via chiral auxiliary (bicyclic lactam) controlled SNAr reactions.

    PubMed

    Sen, Subhabrata; Potti, Venkata R; Surakanti, Ramu; Murthy, Y L N; Pallepogu, Raghavaiah

    2011-01-21

    A highly efficient enantioselective S(N)Ar reaction of chiral acyl bicyclic lactam with substituted-2,4-dinitrobenzenes was developed, affording products containing quarternary stereogenic centers. They are further utilized towards an enantioselective synthesis of spirooxoindoles.

  19. A Robust and Versatile Method of Combinatorial Chemical Synthesis of Gene Libraries via Hierarchical Assembly of Partially Randomized Modules

    PubMed Central

    Popova, Blagovesta; Schubert, Steffen; Bulla, Ingo; Buchwald, Daniela; Kramer, Wilfried

    2015-01-01

    A major challenge in gene library generation is to guarantee a large functional size and diversity that significantly increases the chances of selecting different functional protein variants. The use of trinucleotides mixtures for controlled randomization results in superior library diversity and offers the ability to specify the type and distribution of the amino acids at each position. Here we describe the generation of a high diversity gene library using tHisF of the hyperthermophile Thermotoga maritima as a scaffold. Combining various rational criteria with contingency, we targeted 26 selected codons of the thisF gene sequence for randomization at a controlled level. We have developed a novel method of creating full-length gene libraries by combinatorial assembly of smaller sub-libraries. Full-length libraries of high diversity can easily be assembled on demand from smaller and much less diverse sub-libraries, which circumvent the notoriously troublesome long-term archivation and repeated proliferation of high diversity ensembles of phages or plasmids. We developed a generally applicable software tool for sequence analysis of mutated gene sequences that provides efficient assistance for analysis of library diversity. Finally, practical utility of the library was demonstrated in principle by assessment of the conformational stability of library members and isolating protein variants with HisF activity from it. Our approach integrates a number of features of nucleic acids synthetic chemistry, biochemistry and molecular genetics to a coherent, flexible and robust method of combinatorial gene synthesis. PMID:26355961

  20. Biochemical Characterization of Porphobilinogen Deaminase–Deficient Mice During Phenobarbital Induction of Heme Synthesis and the Effect of Enzyme Replacement

    PubMed Central

    Johansson, Annika; Möller, Christer; Fogh, Jens; Harper, Pauline

    2003-01-01

    Acute intermittent porphyria (AIP) is a genetic disorder caused by a deficiency of porphobilinogen deaminase (PBGD), the 3rd enzyme in heme synthesis. It is clinically characterized by acute attacks of neuropsychiatric symptoms and biochemically by increased urinary excretion of the porphyrin precursors porphobilinogen (PBG) and 5-aminolevulinic acid (ALA). A mouse model that is partially deficient in PBGD and biochemically mimics AIP after induction of the hepatic ALA synthase by phenobarbital was used in this study to identify the site of formation of the presumably toxic porphyrin precursors and study the effect of enzyme-replacement therapy by using recombinant human PBGD (rhPBGD). After 4 d of phenobarbital administration, high levels of PBG and ALA were found in liver, kidney, plasma, and urine of the PBGD-deficient mice. The administration of rhPBGD intravenously or subcutaneously after a 4-d phenobarbital induction was shown to lower the PBG level in plasma in a dose-dependent manner with maximal effect seen after 30 min and 2 h, respectively. Injection of rhPBGD subcutaneously twice daily during a 4-d phenobarbital induction reduced urinary PBG excretion to 25% of the levels found in PBGD-deficient mice administered with only phenobarbital. This study points to the liver as the main producer of PBG and ALA in the phenobarbital-induced PBGD-deficient mice and demonstrates efficient removal of accumulated PBG in plasma and urine by enzyme-replacement therapy. PMID:15208740

  1. A Robust and Versatile Method of Combinatorial Chemical Synthesis of Gene Libraries via Hierarchical Assembly of Partially Randomized Modules.

    PubMed

    Popova, Blagovesta; Schubert, Steffen; Bulla, Ingo; Buchwald, Daniela; Kramer, Wilfried

    2015-01-01

    A major challenge in gene library generation is to guarantee a large functional size and diversity that significantly increases the chances of selecting different functional protein variants. The use of trinucleotides mixtures for controlled randomization results in superior library diversity and offers the ability to specify the type and distribution of the amino acids at each position. Here we describe the generation of a high diversity gene library using tHisF of the hyperthermophile Thermotoga maritima as a scaffold. Combining various rational criteria with contingency, we targeted 26 selected codons of the thisF gene sequence for randomization at a controlled level. We have developed a novel method of creating full-length gene libraries by combinatorial assembly of smaller sub-libraries. Full-length libraries of high diversity can easily be assembled on demand from smaller and much less diverse sub-libraries, which circumvent the notoriously troublesome long-term archivation and repeated proliferation of high diversity ensembles of phages or plasmids. We developed a generally applicable software tool for sequence analysis of mutated gene sequences that provides efficient assistance for analysis of library diversity. Finally, practical utility of the library was demonstrated in principle by assessment of the conformational stability of library members and isolating protein variants with HisF activity from it. Our approach integrates a number of features of nucleic acids synthetic chemistry, biochemistry and molecular genetics to a coherent, flexible and robust method of combinatorial gene synthesis.

  2. Ectoines as compatible solutes and carbon and energy sources for the halophilic bacterium Chromohalobacter salexigens.

    PubMed

    Vargas, C; Jebbar, M; Carrasco, R; Blanco, C; Calderón, M I; Iglesias-Guerra, F; Nieto, J J

    2006-01-01

    To investigate the catabolism of ectoine and hydroxyectoine, which are the major compatible solutes synthesized by Chromohalobacter salexigens. Growth curves performed in M63 minimal medium with low (0.75 mol l(-1) NaCl), optimal (1.5 mol l(-1) NaCl) or high (2.5 mol l(-1) NaCl) salinity revealed that betaine and ectoines were used as substrate for growth at optimal and high salt. Ectoine transport was maximal at optimal salinity, and showed 3- and 1.5-fold lower values at low and high salinity respectively. The salt-sensitive ectA mutant CHR62 showed an ectoine transport rate 6.8-fold higher than that of the wild type. Incubation of C. salexigens in a mixture of glucose and ectoine resulted in a biphasic growth pattern. However, CO(2) production due to ectoine catabolism was lower, but not completely abolished, in the presence of glucose. When used as the sole carbon source, glycine betaine effectively inhibited ectoine and hydroxyectoine synthesis at any salinity. The catabolic pathways for ectoine and hydroxyectoine in C. salexigens operate at optimal and high (although less efficiently) salinity. Endogenous ectoine(s) may repress its own transport. Ectoine utilization was only partially repressed by glucose. Betaine, when used as carbon source, suppresses synthesis of ectoines even under high osmolarity conditions. This study is a previous step to the subsequent isolation and manipulation of the catabolic genes, so as to generate strains with enhanced production of ectoine and hydroxyectoine.

  3. One-pot green synthesis of doxorubicin loaded-silica nanoparticles for in vivo cancer therapy.

    PubMed

    Jiang, Shan; Hua, Li; Guo, Zilong; Sun, Lin

    2018-09-01

    The present work reveals a new and simple one-pot green method to load doxorubicin (DOX) drugs in silica nanoparticles for efficient in vivo cancer therapy. The synthesis of DOX loaded silica nanoparticles (SiNPs/DOX) is based on the efficient encapsulation of DOX in surfactant Tween 80 micelles which act as a template for the formation of silica nanoparticles. The release profile, cellular uptake behavior, cytotoxicity and antitumor effect of SiNPs/DOX nanoparticles were investigated and compared to free DOX. The silica nanoparticles improved the cellular drug delivery efficiency and exhibited high cytotoxicity, successfully achieving the inhibition of tumor growth. Notably, the tumor size and weight of SiNPs/DOX group was 2-fold and 1.7-fold smaller than that of free DOX group, and 4-fold and 2-fold smaller than that of PBS group. The one-pot green synthesis system may have the potential to be developed as a promising drug delivery system. Copyright © 2018 Elsevier B.V. All rights reserved.

  4. Palladium-catalyzed one-pot three- or four-component coupling of aryl iodides, alkynes, and amines through C-N bond cleavage: efficient synthesis of indole derivatives.

    PubMed

    Hao, Wei; Geng, Weizhi; Zhang, Wen-Xiong; Xi, Zhenfeng

    2014-02-24

    An efficient synthesis of N-substituted indole derivatives was realized by combining the Pd-catalyzed one-pot multicomponent coupling approach with cleavage of the C(sp(3))-N bonds. Three or four components of aryl iodides, alkynes, and amines were involved in this coupling process. The cyclopentadiene-phosphine ligand showed high efficiency. A variety of aryl iodides, including cyclic and acyclic tertiary amino aryl iodides, and substituted 1-bromo-2-iodobenzene derivatives could be used. Both symmetric and unsymmetric alkynes substituted with alkyl, aryl, or trimethylsilyl groups could be applied. Cyclic secondary amines such as piperidine, morpholine, 4-methylpiperidine, 1-methylpiperazine, 2-methylpiperidine, and acyclic amines including secondary and primary amines all showed good reactivity. Further application of the resulting indole derivatives was demonstrated by the synthesis of benzosilolo[2,3-b]indole. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Synthesis of 1,4-amino alcohols by Grignard reagent addition to THF and N-tosyliminobenzyliodinane.

    PubMed

    Tejo, Ciputra; See, Yang Feng Anders; Mathiew, Mitch; Chan, Philip Wai Hong

    2016-01-21

    The synthesis of 1,4-amino alcohols from THF treated with N-tosyliminobenzyliodinane (PhINTs) followed by a Grignard reagent under mild reaction conditions at room temperature is described herein. Various Grignard reagents were shown to be compatible, furnishing the corresponding 4-substituted-N-1,4-tosylamino alcohols in good to excellent yields. A partial or full detosylation of the N-tosyl-1,4-amino alcohol was observed in instances involving a sterically bulky Grignard reagent, leading to the deprotected 1,4-amino alcohol product in moderate to good yields. The synthetic utility of this protocol was demonstrated by the synthesis of a 5-substituted-N-tosyl-1,5-amino alcohol from THP and the conversion of two examples to their corresponding γ-lactam and pyrrolidine adducts.

  6. Synthesis of carbon nanotubes from waste polyethylene plastics

    NASA Astrophysics Data System (ADS)

    Zhuo, Chuanwei

    Generation of non-biodegradable wastes, such as plastics, and resulting land as well as water pollution therefrom discarded plastics have been continuously increasing, while landfill space decreases and recycling markets dwindle. Exploration of novel uses of such materials becomes therefore imperative. Here I present an innovative and unique partial conversion of plastic waste to valuable carbon nanomaterials. It is an overall exothermic and scalable process based on feeding waste plastics to a multi-stage, pyrolysis/combustion-synthesis reactor. Plain stainless steel screens are used as substrates as well as low-cost catalyst for both carbon nanomaterials synthesis and pyrolyzates generation. Nano carbon yields of as high as 13.6% of the weight of the polymer precursor were recorded. This demonstration provides a sustainable solution to both plastic waste utilization, and carbon nanomaterials mass production.

  7. Total Synthesis of Bryostatins. Development of Methodology for Atom-Economic and Stereoselective Synthesis of the C-ring Subunit

    PubMed Central

    Trost, Barry M.; Frontier, Alison J.; Thiel, Oliver R.; Yang, Hanbiao; Dong, Guangbin

    2012-01-01

    Bryostatins, a family of structurally complicated macrolides, exhibit an exceptional range of biological activities. The limited availability and structural complexity of these molecules makes development of an efficient total synthesis particularly important. This article describes our initial efforts towards the total synthesis of bryostatins, in which chemoselective and atom-economical methods for stereoselective assembly of the C-ring subunit were developed. A Pd-catalyzed tandem alkyne-alkyne coupling/6-endo-dig cyclization sequence was explored and successfully pursued in the synthesis of a dihydropyran ring system. Elaboration of this methodology ultimately led to a concise synthesis of the C-ring subunit of bryostatins. PMID:21793057

  8. 75 FR 9442 - Lonza, Inc., Riverside Plant, Lonza Exclusive Synthesis Section, Custom Manufacturing Division...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2010-03-02

    ... competitive with cGMP intermediates and Active Pharmaceutical Ingredients from the subject facility to a..., Conshohocken, Pennsylvania, who are engaged in employment related to the production of cGMP intermediates and...GMP intermediates and Active Pharmaceutical Ingredients, who became totally or partially separated...

  9. Polyploidization without mitosis improves in vivo liver transduction with lentiviral vectors.

    PubMed

    Pichard, Virginie; Couton, Dominique; Desdouets, Chantal; Ferry, Nicolas

    2013-02-01

    Lentiviral vectors are efficient gene delivery vehicles for therapeutic and research applications. In contrast to oncoretroviral vectors, they are able to infect most nonproliferating cells. In the liver, induction of cell proliferation dramatically improved hepatocyte transduction using all types of retroviral vectors. However, the precise relationship between hepatocyte division and transduction efficiency has not been determined yet. Here we compared gene transfer efficiency in the liver after in vivo injection of recombinant lentiviral or Moloney murine leukemia viral (MoMuLV) vectors in hepatectomized rats treated or not with retrorsine, an alkaloid that blocks hepatocyte division and induces megalocytosis. Partial hepatectomy alone resulted in a similar increase in hepatocyte transduction using either vector. In retrorsine-treated and partially hepatectomized rats, transduction with MoMuLV vectors dropped dramatically. In contrast, we observed that retrorsine treatment combined with partial hepatectomy increased lentiviral transduction to higher levels than hepatectomy alone. Analysis of nuclear ploidy in single cells showed that a high level of transduction was associated with polyploidization. In conclusion, endoreplication could be exploited to improve the efficiency of liver-directed lentiviral gene therapy.

  10. Polyploidization Without Mitosis Improves In Vivo Liver Transduction With Lentiviral Vectors

    PubMed Central

    Couton, Dominique; Desdouets, Chantal; Ferry, Nicolas

    2013-01-01

    Abstract Lentiviral vectors are efficient gene delivery vehicles for therapeutic and research applications. In contrast to oncoretroviral vectors, they are able to infect most nonproliferating cells. In the liver, induction of cell proliferation dramatically improved hepatocyte transduction using all types of retroviral vectors. However, the precise relationship between hepatocyte division and transduction efficiency has not been determined yet. Here we compared gene transfer efficiency in the liver after in vivo injection of recombinant lentiviral or Moloney murine leukemia viral (MoMuLV) vectors in hepatectomized rats treated or not with retrorsine, an alkaloid that blocks hepatocyte division and induces megalocytosis. Partial hepatectomy alone resulted in a similar increase in hepatocyte transduction using either vector. In retrorsine-treated and partially hepatectomized rats, transduction with MoMuLV vectors dropped dramatically. In contrast, we observed that retrorsine treatment combined with partial hepatectomy increased lentiviral transduction to higher levels than hepatectomy alone. Analysis of nuclear ploidy in single cells showed that a high level of transduction was associated with polyploidization. In conclusion, endoreplication could be exploited to improve the efficiency of liver-directed lentiviral gene therapy. PMID:23249390

  11. A Tunable Bimetallic MOF-74 for Adsorption Chiller Applications: A Tunable Bimetallic MOF-74 for Adsorption Chiller Applications

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

    Liu, Jian; Zheng, Jian; Barpaga, Dushyant

    A mixed metal strategy, in which two different metal nodes coexist in one MOF framework, was examined using MOF-74. The Ni salt precursor for the MOF-74(Ni) analogue was partially replaced during synthesis with relatively inexpensive Zn salt. These bimetallic MOFs were developed and examined for water sorption for potential use in adsorption cooling/chiller applications. Varying concentration ratios of Ni:Zn in MOF-74 achieved using this mixed metal strategy were shown to provide unique impacts on H2O uptake while significantly mitigating the costs of synthesis

  12. Development of a gene synthesis platform for the efficient large scale production of small genes encoding animal toxins.

    PubMed

    Sequeira, Ana Filipa; Brás, Joana L A; Guerreiro, Catarina I P D; Vincentelli, Renaud; Fontes, Carlos M G A

    2016-12-01

    Gene synthesis is becoming an important tool in many fields of recombinant DNA technology, including recombinant protein production. De novo gene synthesis is quickly replacing the classical cloning and mutagenesis procedures and allows generating nucleic acids for which no template is available. In addition, when coupled with efficient gene design algorithms that optimize codon usage, it leads to high levels of recombinant protein expression. Here, we describe the development of an optimized gene synthesis platform that was applied to the large scale production of small genes encoding venom peptides. This improved gene synthesis method uses a PCR-based protocol to assemble synthetic DNA from pools of overlapping oligonucleotides and was developed to synthesise multiples genes simultaneously. This technology incorporates an accurate, automated and cost effective ligation independent cloning step to directly integrate the synthetic genes into an effective Escherichia coli expression vector. The robustness of this technology to generate large libraries of dozens to thousands of synthetic nucleic acids was demonstrated through the parallel and simultaneous synthesis of 96 genes encoding animal toxins. An automated platform was developed for the large-scale synthesis of small genes encoding eukaryotic toxins. Large scale recombinant expression of synthetic genes encoding eukaryotic toxins will allow exploring the extraordinary potency and pharmacological diversity of animal venoms, an increasingly valuable but unexplored source of lead molecules for drug discovery.

  13. Improved transcription and translation with L-leucine stimulation of mTORC1 in Roberts syndrome.

    PubMed

    Xu, Baoshan; Gogol, Madelaine; Gaudenz, Karin; Gerton, Jennifer L

    2016-01-05

    Roberts syndrome (RBS) is a human developmental disorder caused by mutations in the cohesin acetyltransferase ESCO2. We previously reported that mTORC1 signaling was depressed and overall translation was reduced in RBS cells and zebrafish models for RBS. Treatment of RBS cells and zebrafish RBS models with L-leucine partially rescued mTOR function and protein synthesis, correlating with increased cell division and improved development. In this study, we use RBS cells to model mTORC1 repression and analyze transcription and translation with ribosome profiling to determine gene-level effects of L-leucine. L-leucine treatment partially rescued translational efficiency of ribosomal subunits, translation initiation factors, snoRNA production, and mitochondrial function in RBS cells, consistent with these processes being mTORC1 controlled. In contrast, other genes are differentially expressed independent of L-leucine treatment, including imprinted genes such as H19 and GTL2, miRNAs regulated by GTL2, HOX genes, and genes in nucleolar associated domains. Our study distinguishes between gene expression changes in RBS cells that are TOR dependent and those that are independent. Some of the TOR independent gene expression changes likely reflect the architectural role of cohesin in chromatin looping and gene expression. This study reveals the dramatic rescue effects of L-leucine stimulation of mTORC1 in RBS cells and supports that normal gene expression and translation requires ESCO2 function.

  14. Chemical Synthesis of Complex Molecules Using Nanoparticle Catalysis

    PubMed Central

    Cong, Huan; Porco, John A.

    2011-01-01

    Nanoparticle catalysis has emerged as an active topic in organic synthesis. Of particular interest is the development of enabling methodologies to efficiently assemble complex molecules using nanoparticle catalysis. This Viewpoint highlights recent developments and discusses future perspectives in this emerging field. PMID:22347681

  15. A synthesis of the "state-of-the-practice for advancing planning and operations integration opportunities within transportation agencies".

    DOT National Transportation Integrated Search

    2014-12-01

    Linking Planning and Operations is vital to improving transportation decision-making and overall : efficiency of transportation systems management. This synthesis summarizes current state of : knowledge and practices in Planning and Operations Integr...

  16. Efficient synthesis of phosphatidylserine in 2-methyltetrahydrofuran.

    PubMed

    Duan, Zhang-Qun; Hu, Fei

    2013-01-10

    2-Methyltetrahydrofuran has recently been described as a promising and green solvent. Herein, it was successfully used as the reaction medium for enzyme-mediated transphosphatidylation of phosphatidylcholine with L-serine with the aim of phosphatidylserine synthesis for the first time. Our results indicated that as high as 90% yield of phosphatidylserine could be achieved after 12 h combined with no byproduct (phosphatidic acid) forming. The present work accommodated a facilely and efficiently enzymatic strategy for preparing phosphatidylserine, which possessed obvious advantages over the reported processes in terms of high efficiency and environmental friendliness. This work is also a proof-of-concept opening the use of 2-methyltetrahydrofuran in biosynthesis as well. Copyright © 2012 Elsevier B.V. All rights reserved.

  17. Are Polyphosphates or Phosphate Esters Prebiotic Reagents?

    NASA Technical Reports Server (NTRS)

    Keefe, Anthony D.; Miller, Stanley L.

    1995-01-01

    It is widely held that there was a phosphate compound in prebiotic chemistry that played the role of adenosine triphosphate and that the first living organisms had ribose-phosphate in the backbone of their genetic material. However, there are no known efficient prebiotic synthesis of high-energy phosphates or phosphate esters. We review the occurrence of phosphates in nature, the efficiency of the volcanic synthesis of P4O10, the efficiency of polyphosphate synthesis by heating phosphate minerals under geological conditions, and the use of high-energy organic compounds such as cyanamide or hydrogen cyanide. These are shown to be inefficient processes especially when the hydrolysis of the polyphosphates is taken into account. For example, if a whole atmosphere of methane or carbon monoxide were converted to cyanide which somehow synthesized polyphosphates quantitatively, the polyphosphate concentration in the ocean would still have been insignificant. We also attempted to find more efficient high-energy polymerizing agents by spark discharge syntheses, but without success. There may still be undiscovered robust prebiotic syntheses of polyphosphates, or mechanisms for concentrating them, but we conclude that phosphate esters may not have been constituents of the first genetic material. Phosphoanhydrides are also unlikely as prebiotic energy sources.

  18. Improvement of the BiOI photocatalytic activity optimizing the solvothermal synthesis

    NASA Astrophysics Data System (ADS)

    Mera, Adriana C.; Moreno, Yanko; Contreras, David; Escalona, Nestor; Meléndrez, Manuel F.; Mangalaraja, Ramalinga Viswanathan; Mansilla, Héctor D.

    2017-01-01

    BiOI nanostructured microspheres were obtained from the solvothermal synthesis route in the presence of ethylene glycol and KI as solvent and source of iodide, respectively. Optimal conditions for the synthesis were obtained by using multivariate analysis and choosing the photocatalytic oxidation rate constant of 3,4,5-trihydroxybenzoic acid (gallic acid) as response factor under simulated solar radiation. Response surface methodology (RSM) was used to determine the optimum values of the reaction time and temperature which were 18 h and 126 °C, respectively, to obtain the most active catalyst. In addition, BiOI synthesis using ionic liquid 1-butyl-3-methylimidazolium iodide ([bmim]I) as iodide source was also carried out for the comparison of microstructure and its photocatalytic efficiency. The obtained BiOI nanostructures were characterized by scanning electron microscopy (SEM) attached with energy dispersive spectrometer (EDS), nitrogen adsorption, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), thermogravimetry (TG), Fourier transform infrared (FTIR) spectrometry, diffuse reflectance spectroscopy (DRS) and cyclic voltammetry (CV) analyses for their changes in morphological and structural behaviors. It was observed that the synthesis temperature of BiOI nanostructures strongly influenced the morphology, crystalline phase, surface area and electrochemical behavior, and thus affecting the photocatalytic efficiency. The higher photocatalytic removal of gallic acid (60%) was reached within 30 min of irradiation with UV-A on microspheres obtained with ionic liquid. The (1 1 0) crystal phase of BiOI influenced the photocatalytic efficiency.

  19. Facile bottom-up synthesis of partially oxidized black phosphorus nanosheets as metal-free photocatalyst for hydrogen evolution

    PubMed Central

    Tian, Bin; Tian, Bining; Smith, Bethany; Scott, M. C.; Lei, Qin; Hua, Ruinian; Liu, Yi

    2018-01-01

    Few-layer black phosphorus (BP) nanosheets were first reported as a 2D material for the application of field-effect transistors in 2014 and have stimulated intense activity among physicists, chemists, and material and biomedical scientists, driving research into novel synthetic techniques to produce BP nanosheets. At present, exfoliation is the main route toward few-layer BP nanosheets via employing bulk BP as raw material. However, this is a complicated and time-consuming process, which is difficult for the large-scale synthesis of BP nanosheets. Moreover, BP degrades rapidly when exfoliated to nanoscale dimensions, resulting in the rapid loss of semiconducting properties. Here, we report the direct wet-chemical synthesis of few-layer BP nanosheets in gram-scale quantities in a bottom-up approach based on common laboratory reagents at low temperature, showing excellent stability due to partial oxidation of surface. Solvent and temperature are two critical factors, controlling not only the formation of BP nanosheets but also the thickness. The as-prepared BP nanosheets can extract hydrogen from pure water (pH = 6.8), exhibiting more than 24-fold higher activity than the well-known C3N4 nanosheets. Our results reporting the ability to prepare few-layer BP nanosheets with a facile, scalable, low-cost approach take us a step closer to real-world applications of phosphorene including next-generation metal-free photocatalysts for photosynthesis. PMID:29563225

  20. Blind separation of overlapping partials in harmonic musical notes using amplitude and phase reconstruction

    NASA Astrophysics Data System (ADS)

    de León, Jesús Ponce; Beltrán, José Ramón

    2012-12-01

    In this study, a new method of blind audio source separation (BASS) of monaural musical harmonic notes is presented. The input (mixed notes) signal is processed using a flexible analysis and synthesis algorithm (complex wavelet additive synthesis, CWAS), which is based on the complex continuous wavelet transform. When the harmonics from two or more sources overlap in a certain frequency band (or group of bands), a new technique based on amplitude similarity criteria is used to obtain an approximation to the original partial information. The aim is to show that the CWAS algorithm can be a powerful tool in BASS. Compared with other existing techniques, the main advantages of the proposed algorithm are its accuracy in the instantaneous phase estimation, its synthesis capability and that the only input information needed is the mixed signal itself. A set of synthetically mixed monaural isolated notes have been analyzed using this method, in eight different experiments: the same instrument playing two notes within the same octave and two harmonically related notes (5th and 12th intervals), two different musical instruments playing 5th and 12th intervals, two different instruments playing non-harmonic notes, major and minor chords played by the same musical instrument, three different instruments playing non-harmonically related notes and finally the mixture of a inharmonic instrument (piano) and one harmonic instrument. The results obtained show the strength of the technique.

  1. Process for the synthesis of aliphatic alcohol-containing mixtures

    DOEpatents

    Greene, Marvin I.; Gelbein, Abraham P.

    1984-01-01

    A process for the synthesis of mixtures which include saturated aliphatic alcohols is disclosed. In the first step of the process, the first catalyst activation stage, a catalyst, which comprises the oxides of copper, zinc, aluminum, potassium and one or two additional metals selected from the group consisting of chromium, magnesium, cerium, cobalt, thorium and lanthanum, is partially activated. In this step, a reducing gas stream, which includes hydrogen and at least one inert gas, flows past the catalyst at a space velocity of up to 5,000 liters (STP) per hour, per kilogram of catalyst. The partially activated catalyst is then subjected to the second step of the process, second-stage catalyst activation. In this step, the catalyst is contacted by an activation gas stream comprising hydrogen and carbon monoxide present in a volume ratio of 0.5:1 and 4:1, respectively, at a temperature of 200.degree. to 450.degree. C. and a pressure of between 35 and 200 atmospheres. The activation gas flows at a space velocity of from 1,000 to 20,000 liters (STP) per hour, per kilogram of catalyst. Second-stage activation continues until the catalyst is contacted with at least 500,000 liters (STP) of activation gas per kilogram of catalyst. The fully activated catalyst, in the third step of the process, contacts a synthesis gas stream comprising hydrogen and carbon monoxide.

  2. Process for the synthesis of aliphatic alcohol-containing mixtures

    DOEpatents

    Greene, M.I.; Gelbein, A.P.

    1984-10-16

    A process for the synthesis of mixtures which include saturated aliphatic alcohols is disclosed. In the first step of the process, the first catalyst activation stage, a catalyst, which comprises the oxides of copper, zinc, aluminum, potassium and one or two additional metals selected from the group consisting of chromium, magnesium, cerium, cobalt, thorium and lanthanum, is partially activated. In this step, a reducing gas stream, which includes hydrogen and at least one inert gas, flows past the catalyst at a space velocity of up to 5,000 liters (STP) per hour, per kilogram of catalyst. The partially activated catalyst is then subjected to the second step of the process, second-stage catalyst activation. In this step, the catalyst is contacted by an activation gas stream comprising hydrogen and carbon monoxide present in a volume ratio of 0.5:1 and 4:1, respectively, at a temperature of 200 to 450 C and a pressure of between 35 and 200 atmospheres. The activation gas flows at a space velocity of from 1,000 to 20,000 liters (STP) per hour, per kilogram of catalyst. Second-stage activation continues until the catalyst is contacted with at least 500,000 liters (STP) of activation gas per kilogram of catalyst. The fully activated catalyst, in the third step of the process, contacts a synthesis gas stream comprising hydrogen and carbon monoxide.

  3. Synthesis and Characterization of Hexagonal Boron Nitride as a Gate Dielectric

    PubMed Central

    Jang, Sung Kyu; Youn, Jiyoun; Song, Young Jae; Lee, Sungjoo

    2016-01-01

    Two different growth modes of large-area hexagonal boron nitride (h-BN) film, a conventional chemical vapor deposition (CVD) growth mode and a high-pressure CVD growth mode, were compared as a function of the precursor partial pressure. Conventional self-limited CVD growth was obtained below a critical partial pressure of the borazine precursor, whereas a thick h-BN layer (thicker than a critical thickness of 10 nm) was grown beyond a critical partial pressure. An interesting coincidence of a critical thickness of 10 nm was identified in both the CVD growth behavior and in the breakdown electric field strength and leakage current mechanism, indicating that the electrical properties of the CVD h-BN film depended significantly on the film growth mode and the resultant film quality. PMID:27458024

  4. Developing Inhibitors of Translesion DNA Synthesis as Therapeutic Agents against Lung Cancer

    DTIC Science & Technology

    2015-12-01

    normal DNA synthesis. In contrast, pol eta shows a combination of high efficiency and low fidelity when replicating 8-oxo-G. These combined properties...are consistent with a pro- mutagenic role for pol eta when replicating this DNA lesion under cellular conditions. Studies with modified nucleotide...analogs indicate that pol eta relies heavily on hydrogen-bonding interactions during normal and translesion synthesis. However, some nucleobase

  5. Highly Efficient Flexible Hybrid Photovoltaic Cells Based on Low-Band-Gap Conjugated Polymers Sensitized by Nanoparticle-Grafted Carbon

    DTIC Science & Technology

    2010-09-01

    modeling, synthesis , and characterization of several series functional and processable electro-active conjugated polymers with evolving frontier...tasks as a basic obligation of this award: Task #1. Low Band Gap Polymers The awardee (Professor Sun’s group at NSU) shall design, synthesis , and...design, modeling, synthesis , and characterizations of several series functional and processable electro-active conjugated polymers with evolving

  6. Formal Synthesis of (±)-Aplykurodinone-1 through a Hetero-Pauson-Khand Cycloaddition Approach.

    PubMed

    Tao, Cheng; Zhang, Jing; Chen, Xiaoming; Wang, Huifei; Li, Yun; Cheng, Bin; Zhai, Hongbin

    2017-03-03

    The tricyclic intermediate 2 has been synthesized in eight steps from known compound 6 in 20% overall yield. As such, this constitutes a highly efficient formal synthesis of (±)-aplykurodinone-1. This synthesis features a unique, one-pot, intramolecular hetero-Pauson-Khand reaction (h-PKR)/desilylation sequence to expeditiously construct the tricyclic framework, providing valuable insights for expanding the scope and boundaries of h-PKR.

  7. Scope and Limitations of Fmoc Chemistry SPPS-Based Approaches to the Total Synthesis of Insulin Lispro via Ester Insulin.

    PubMed

    Dhayalan, Balamurugan; Mandal, Kalyaneswar; Rege, Nischay; Weiss, Michael A; Eitel, Simon H; Meier, Thomas; Schoenleber, Ralph O; Kent, Stephen B H

    2017-01-31

    We have systematically explored three approaches based on 9-fluorenylmethoxycarbonyl (Fmoc) chemistry solid phase peptide synthesis (SPPS) for the total chemical synthesis of the key depsipeptide intermediate for the efficient total chemical synthesis of insulin. The approaches used were: stepwise Fmoc chemistry SPPS; the "hybrid method", in which maximally protected peptide segments made by Fmoc chemistry SPPS are condensed in solution; and, native chemical ligation using peptide-thioester segments generated by Fmoc chemistry SPPS. A key building block in all three approaches was a Glu[O-β-(Thr)] ester-linked dipeptide equipped with a set of orthogonal protecting groups compatible with Fmoc chemistry SPPS. The most effective method for the preparation of the 51 residue ester-linked polypeptide chain of ester insulin was the use of unprotected peptide-thioester segments, prepared from peptide-hydrazides synthesized by Fmoc chemistry SPPS, and condensed by native chemical ligation. High-resolution X-ray crystallography confirmed the disulfide pairings and three-dimensional structure of synthetic insulin lispro prepared from ester insulin lispro by this route. Further optimization of these pilot studies could yield an efficient total chemical synthesis of insulin lispro (Humalog) based on peptide synthesis by Fmoc chemistry SPPS. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Quantum communication for satellite-to-ground networks with partially entangled states

    NASA Astrophysics Data System (ADS)

    Chen, Na; Quan, Dong-Xiao; Pei, Chang-Xing; Yang-Hong

    2015-02-01

    To realize practical wide-area quantum communication, a satellite-to-ground network with partially entangled states is developed in this paper. For efficiency and security reasons, the existing method of quantum communication in distributed wireless quantum networks with partially entangled states cannot be applied directly to the proposed quantum network. Based on this point, an efficient and secure quantum communication scheme with partially entangled states is presented. In our scheme, the source node performs teleportation only after an end-to-end entangled state has been established by entanglement swapping with partially entangled states. Thus, the security of quantum communication is guaranteed. The destination node recovers the transmitted quantum bit with the help of an auxiliary quantum bit and specially defined unitary matrices. Detailed calculations and simulation analyses show that the probability of successfully transferring a quantum bit in the presented scheme is high. In addition, the auxiliary quantum bit provides a heralded mechanism for successful communication. Based on the critical components that are presented in this article an efficient, secure, and practical wide-area quantum communication can be achieved. Project supported by the National Natural Science Foundation of China (Grant Nos. 61072067 and 61372076), the 111 Project (Grant No. B08038), the Fund from the State Key Laboratory of Integrated Services Networks (Grant No. ISN 1001004), and the Fundamental Research Funds for the Central Universities (Grant Nos. K5051301059 and K5051201021).

  9. Liver nuclear DNA synthesis in mice following carbon tetrachloride administration or partial hepatectomy

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

    Gans, J.H.; Korson, R.

    1984-02-01

    Long-term, continuous (twice per week) administration of CCl/sub 4/ to male mice resulted in a high incidence of liver nodules which appear to be resistant to the necrotizing effects of CCl/sub 4/ but showed no features of malignant neoplasia. Liver nuclear DNA synthesis was compared in mice given CCl/sub 4/ and in mice subjected to partial hepatectomy (PH). Mice were given by gavage corn oil or CCl/sub 4/ in corn oil for periods of 2 to 25 weeks and several mice were subjected to PH after 12 and 25 weeks of corn oil treatment. Mice were given (/sup 3/H)TdR duringmore » liver regeneration and newly synthesized liver nuclear DNA was isolated and separated by BND-cellulose chromatography. Greater than 85% of the labeled DNA from PH mice eluted from BND-cellulose columns as double-stranded (ds) DNA with single-stranded (ss) regions or ends and less than 15% as ds DNA. When mice were treated with CCl/sub 4/ for 8 weeks or longer a significantly greater portion of liver nuclear DNA eluted as ds DNA. Administration of HU and 5-FU with (/sup 3/H)TdR decreased (/sup 3/H)TdR incorporation into DNA to low levels incompatible with unscheduled DNA synthesis. Single doses of CCl/sub 4/ given to mice treated with corn oil for 2 to 12 weeks provided newly synthesized DNA which was primarily (>80%) ds DNA with ss regions or ends, but after 25 weeks of corn oil administration, a single dose of CCl/sub 4/ resulted in newly synthesized DNA with a greater proportion of ds DNA. The high labeling of ds DNA in mice treated with CCl/sub 4/ may have resulted from an alternate pathway of DNA synthesis catalyzed by the enzymes or enzyme complexes associated with semiconservative DNA synthesis or from proliferation of nonparenchymal cells with a rapid turn-over rate.« less

  10. An efficient synthesis of tetramic acid derivatives with extended conjugation from L-Ascorbic Acid

    PubMed Central

    Singh, Biswajit K; Bisht, Surendra S; Tripathi, Rama P

    2006-01-01

    Background Tetramic acids with polyenyl substituents are an important class of compounds in medicinal chemistry. Both solid and solution phase syntheses of such molecules have been reported recently. Thiolactomycin, a clinical candidate for treatment of tuberculosis has led to further explorations in this class. We have recently developed an efficient synthesis of tetramic acids derivatives from L- ascorbic acid. In continuation of this work, we have synthesised dienyl tetramic acid derivatives. Results 5,6-O-Isopropylidene-ascorbic acid on reaction with DBU led to the formation of tetronolactonyl allyl alcohol, which on oxidation with pyridinium chlorochromate gave the respective tetranolactonyl allylic aldehydes. Wittig olefination followed by reaction of the resulting tetranolactonyl dienyl esters with different amines resulted in the respective 5-hydroxy lactams. Subsequent dehydration of the hydroxy lactams with p-toluene sulphonic acid afforded the dienyl tetramic acid derivatives. All reactions were performed at ambient temperature and the yields are good. Conclusion An efficient and practical method for the synthesis of dienyl tetramic acid derivatives from inexpensive and easily accessible ascorbic acid has been developed. The compounds bear structural similarities to the tetramic acid based polyenic antibiotics and thus this method offers a new and short route for the synthesis of tetramic acid derivatives of biological significance. PMID:17147830

  11. An efficient synthesis of tetramic acid derivatives with extended conjugation from L-ascorbic acid.

    PubMed

    Singh, Biswajit K; Bisht, Surendra S; Tripathi, Rama P

    2006-12-06

    Tetramic acids with polyenyl substituents are an important class of compounds in medicinal chemistry. Both solid and solution phase syntheses of such molecules have been reported recently. Thiolactomycin, a clinical candidate for treatment of tuberculosis has led to further explorations in this class. We have recently developed an efficient synthesis of tetramic acids derivatives from L-ascorbic acid. In continuation of this work, we have synthesised dienyl tetramic acid derivatives. 5,6-O-isopropylidene-ascorbic acid on reaction with DBU led to the formation of tetronolactonyl allyl alcohol, which on oxidation with pyridinium chlorochromate gave the respective tetranolactonyl allylic aldehydes. Wittig olefination followed by reaction of the resulting tetranolactonyl dienyl esters with different amines resulted in the respective 5-hydroxy lactams. Subsequent dehydration of the hydroxy lactams with p-toluene sulphonic acid afforded the dienyl tetramic acid derivatives. All reactions were performed at ambient temperature and the yields are good. An efficient and practical method for the synthesis of dienyl tetramic acid derivatives from inexpensive and easily accessible ascorbic acid has been developed. The compounds bear structural similarities to the tetramic acid based polyenic antibiotics and thus this method offers a new and short route for the synthesis of tetramic acid derivatives of biological significance.

  12. A concise synthesis of benzimidazoles via the microwave-assisted one-pot batch reaction of amino acids up to a 10-g scale.

    PubMed

    Peng, Pai; Xiong, Jin-Feng; Mo, Guang-Zhen; Zheng, Jia-Li; Chen, Ren-Hong; Chen, Xiao-Yun; Wang, Zhao-Yang

    2014-10-01

    An efficient method for the synthesis of aminomethyl benzimidazoles is developed by using a one-pot batch reaction between amino acids and o-phenylenediamines. This reaction proceeds smoothly in an unmodified household microwave oven, even though scale-up is to 10 g. A desirable method for the quick synthesis of benzimidazoles, which are used as a kind of important intermediates in drug synthesis, is provided by the scale-up utilization of amino acid resource.

  13. Measuring partial fluorescence yield using filtered detectors.

    PubMed

    Boyko, T D; Green, R J; Moewes, A; Regier, T Z

    2014-07-01

    Typically, X-ray absorption near-edge structure measurements aim to probe the linear attenuation coefficient. These measurements are often carried out using partial fluorescence yield techniques that rely on detectors having photon energy discrimination improving the sensitivity and the signal-to-background ratio of the measured spectra. However, measuring the partial fluorescence yield in the soft X-ray regime with reasonable efficiency requires solid-state detectors, which have limitations due to the inherent dead-time while measuring. Alternatively, many of the available detectors that are not energy dispersive do not suffer from photon count rate limitations. A filter placed in front of one of these detectors will make the energy-dependent efficiency non-linear, thereby changing the responsivity of the detector. It is shown that using an array of filtered X-ray detectors is a viable method for measuring soft X-ray partial fluorescence yield spectra without dead-time. The feasibility of this technique is further demonstrated using α-Fe2O3 as an example and it is shown that this detector technology could vastly improve the photon collection efficiency at synchrotrons and that these detectors will allow experiments to be completed with a much lower photon flux reducing X-ray-induced damage.

  14. Significant role of Mn(III) sites in e(g)(1) configuration in manganese oxide catalysts for efficient artificial water oxidation.

    PubMed

    Indra, Arindam; Menezes, Prashanth W; Schuster, Felix; Driess, Matthias

    2015-11-01

    Development of efficient bio-inspired water oxidation system with transition metal oxide catalyst has been considered as the one of the most challenging task in the recent years. As the oxygen evolving center of photosystem II consists of Mn4CaO5 cluster, most of the water oxidation study was converged to build up manganese oxide based catalysts. Here we report the synthesis of efficient artificial water oxidation catalysts by transferring the inactive manganese monooxide (MnO) under highly oxidizing conditions with ceric ammonium nitrate (CAN) and ozone (O3). MnO was partially oxidized to form mixed-valent manganese oxide (MnOx) with CAN whereas completely oxidized to mineral phase of ε-MnO2 (Akhtenskite) upon treatment of O3 in acidic solution, which we explore first time as a water oxidation catalyst. Chemical water oxidation, as well as the photochemical water oxidation in the presence of sacrificial electron acceptor and photosensitizer with the presented catalysts were carried out that followed the trends: MnOx>MnO2>MnO. Structural and activity correlation reveals that the presence of larger extent of Mn(III) in MnOx is the responsible factor for higher activity compared to MnO2. Mn(III) species in octahedral system with eg(1) configuration furnishes and facilitates the Mn-O and Mn-Mn bond enlargement with required structural flexibility and disorder in the manganese oxide structure which indeed facilitates water oxidation. Copyright © 2014 Elsevier B.V. All rights reserved.

  15. Stimulation by atropine of acetylcholine release and synthesis in cortical slices from rat brain

    PubMed Central

    Molenaar, P. C.; Polak, R. L.

    1970-01-01

    1. Cortical slices from rat brain were incubated in media containing the irreversible cholinesterase inhibitor soman and a high KCl concentration, and the release and synthesis of acetylcholine (ACh) were determined. 2. Atropine enhanced the release and synthesis of ACh. 3. Tetrodotoxin, a substance which blocks nervous conduction, did not influence the release and synthesis of ACh, in the absence or in the presence of atropine. Therefore the nerve endings are probably the site at which atropine acts when stimulating the release and synthesis of ACh. 4. Pretreatment of the slices with botulinum type A toxin partially blocked the release and synthesis of ACh and reduced the extra amounts of ACh released and synthesized under the influence of atropine. 5. Lowering the calcium or raising the magnesium concentration in the incubation medium reduced the release and synthesis of ACh and their enhancement by atropine. 6. Physostigmine decreased the total extractable ACh content of the slices during incubation in a 25 mM KCl containing medium. This decrease was nearly prevented when the release and synthesis of ACh were inhibited by omission of the calcium ions from the medium, but was enhanced by atropine. 7. The observations made with pretreatment by botulinum type A toxin, with changes in the calcium and magnesium concentration as well as with physostigmine, all support the theory that it is primarily the release of ACh which is enhanced by atropine and that its stimulating action on the synthesis results from the increased release. PMID:5497792

  16. A Student Synthesis of the Housefly Sex Attractant.

    ERIC Educational Resources Information Center

    Cormier, Russell; And Others

    1979-01-01

    A novel and efficient (34 percent overall) multi-step synthesis of the housefly sex attractant, muscalure, is described. Each of the steps involves types of reactions with which the undergraduate student would be familiar after one-and-one-half semesters of organic chemistry. (BB)

  17. Facile synthesis of the cyclohexane fragment of enacloxins, a series of antibiotics isolated from Frateuria sp. W-315.

    PubMed

    Saito, Aki; Igarashi, Wataru; Furukawa, Hiroyuki; Yamada, Teiko; Kuwahara, Shigefumi; Kiyota, Hiromasa

    2014-01-01

    An efficient and good yield synthesis of the cyclohexane moiety of enacyloxins, a series of antibiotics isolated from Frateuria sp. W-315, was achieved from d-quinic acid using a successive Barton-McCombie deoxygenation.

  18. Total Synthesis of Adunctin B.

    PubMed

    Dethe, Dattatraya H; Dherange, Balu D

    2018-03-16

    Total synthesis of (±)-adunctin B, a natural product isolated from Piper aduncum (Piperaceae), has been achieved using two different strategies, in seven and three steps. The efficient approach features highly atom economical and diastereoselective Friedel-Crafts acylation, alkylation reaction and palladium catalyzed Wacker type oxidative cyclization.

  19. Synthesis and toughness properties of resins and composites

    NASA Technical Reports Server (NTRS)

    Johnston, N. J.

    1984-01-01

    Tensile and shear moduli of four ACEE (Aircraft Energy Efficiency Program) resins are presented along with ACEE composite material modulus predictions based on micromechanics. Compressive strength and fracture toughness of the resins and composites were discussed. In addition, several resin synthesis techniques are reviewed.

  20. Flow Chemistry for Designing Sustainable Chemical Synthesis (journal article)

    EPA Science Inventory

    An efficiently designed continuous flow chemical process can lead to significant advantages in developing a sustainable chemical synthesis or process. These advantages are the direct result of being able to impart a higher degree of control on several key reactor and reaction par...

  1. REVISITING NUCLEOPHILIC SUBSTITUTION REACTIONS: MICROWAVE-ASSISTED SYNTHESIS OF AZIDES, THIOCYANATES AND SULFONES IN AQUEOUS MEDIUM

    EPA Science Inventory

    A practical, rapid and efficient microwave (MW) promoted synthesis of various azides, thiocyanates and sulfones, is described in aqueous medium. This general and expeditious MW-enhanced nucleophilic substitution approach uses easily accessible starting materials such as halides o...

  2. NAP enzyme recruitment in simultaneous bioremediation and nanoparticles synthesis.

    PubMed

    Eltarahony, Marwa; Zaki, Sahar; Kheiralla, Zeinab; Abd-El-Haleem, Desouky

    2018-06-01

    The periplasmic nitrate reductase enzyme (NAP) has become attractive catalyst, whose exploitation has emerged as one of the indispensable strategies toward environmentally benign applications. To achieve them efficiently and overcome the sensitivity of NAP in harsh environmental circumstances, the immobilization for denitrifying bacteria and NAP enzyme for simultaneous bioremediation and bionanoparticles synthesis was studied. NAP catalyzed NO 3 - reduction at V max of 0.811 μM/min and K m of 14.02 mM. Concurrently, the immobilized MMT cells completely removed NO 3 - upon 192 h with AgNPs synthesis ranging from 23.26 to 58.14 nm as indicated by SEM. Wherase, immobilized NAP exhibited lower efficiency with 28.6% of NO 3 - elimination within 288 h and large aggregated AgNPs ranging from 94.44 nm to 172.22 nm. To the best of author knowledge, the immobilization for denitrifying bacteria and NAP enzyme for simultaneous bioremediation and bionanoparticles synthesis was not studied before.

  3. Synthesis of palladium nanoparticles with leaf extract of Chrysophyllum cainito (Star apple) and their applications as efficient catalyst for C-C coupling and reduction reactions

    NASA Astrophysics Data System (ADS)

    Majumdar, Rakhi; Tantayanon, Supawan; Bag, Braja Gopal

    2017-10-01

    A simple green chemical method for the one-step synthesis of palladium nanoparticles (PdNPs) has been described by reducing palladium (II) chloride with the leaf extract of Chrysophyllum cainito in aqueous medium. The synthesis of the palladium nanoparticles completed within 2-3 h at room temperature, whereas on heat treatment (70-80 °C), the synthesis of colloidal PdNPs completed almost instantly. The stabilized PdNPs have been characterized in detail by spectroscopic, electron microscopic and light scattering measurements. The synthesized PdNPs have been utilized as a green catalyst for C-C coupling reactions under aerobic and phosphine-free conditions in aqueous medium. In addition, the synthesized PdNPs have also been utilized as a catalyst for a very efficient sodium borohydride reduction of 3- and 4-nitrophenols. The synthesized PdNPs can retain their catalytic activity for several months.

  4. Sustainable and Continuous Synthesis of Enantiopure l-Amino Acids by Using a Versatile Immobilised Multienzyme System.

    PubMed

    Velasco-Lozano, Susana; da Silva, Eunice S; Llop, Jordi; López-Gallego, Fernando

    2018-02-16

    The enzymatic synthesis of α-amino acids is a sustainable and efficient alternative to chemical processes, through which achieving enantiopure products is difficult. To more address this synthesis efficiently, a hierarchical architecture that irreversibly co-immobilises an amino acid dehydrogenase with polyethyleneimine on porous agarose beads has been designed and fabricated. The cationic polymer acts as an irreversible anchoring layer for the formate dehydrogenase. In this architecture, the two enzymes and polymer colocalise across the whole microstructure of the porous carrier. This multifunctional heterogeneous biocatalyst was kinetically characterised and applied to the enantioselective synthesis of a variety of canonical and noncanonical α-amino acids in both discontinuous (batch) and continuous modes. The co-immobilised bienzymatic system conserves more than 50 % of its initial effectiveness after five batch cycles and 8 days of continuous operation. Additionally, the environmental impact of this process has been semiquantitatively calculated and compared with the state of the art. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Synthesis and characterization of natural and modified antifreeze glycopeptides: glycosylated foldamers.

    PubMed

    Nagel, Lilly; Plattner, Carolin; Budke, Carsten; Majer, Zsuzsanna; DeVries, Arthur L; Berkemeier, Thomas; Koop, Thomas; Sewald, Norbert

    2011-08-01

    In Arctic and Antarctic marine regions, where the temperature declines below the colligative freezing point of physiological fluids, efficient biological antifreeze agents are crucial for the survival of polar fish. One group of such agents is classified as antifreeze glycoproteins (AFGP) that usually consist of a varying number (n = 4-55) of [AAT]( n )-repeating units. The threonine side chain of each unit is glycosidically linked to β-D: -galactosyl-(1 → 3)-α-N-acetyl-D: -galactosamine. These biopolymers can be considered as biological antifreeze foldamers. A preparative route for stepwise synthesis of AFGP allows for efficient synthesis. The diglycosylated threonine building block was introduced into the peptide using microwave-enhanced solid phase synthesis. By this versatile solid phase approach, glycosylated peptides of varying sequences and lengths could be obtained. Conformational studies of the synthetic AFGP analogs were performed by circular dichroism experiments (CD). Furthermore, the foldamers were analysed microphysically according to their inhibiting effect on ice recrystallization and influence on the crystal habit.

  6. Synthesis of Resveratrol Tetramers via a Stereoconvergent Radical Equilibrium

    PubMed Central

    Keylor, Mitchell H.; Matsuura, Bryan S.; Griesser, Markus; Chauvin, Jean-Philippe R.; Harding, Ryan A.; Kirillova, Mariia S.; Zhu, Xu; Fischer, Oliver J.; Pratt, Derek A.; Stephenson, Corey R. J.

    2017-01-01

    Persistent free radicals have become indispensable in the synthesis of organic materials by living radical polymerization. However, examples of their use in the synthesis of small molecules are rare. Herein, we report the application of persistent radical and quinone methide intermediates to the synthesis of the resveratrol tetramers nepalensinol B and vateriaphenol C. The spontaneous cleavage and reconstitution of exceptionally weak carbon-carbon bonds has enabled a stereoconvergent oxidative dimerization of racemic materials in a transformation that likely coincides with the biogenesis of these natural products. The efficient synthesis of higher-order oligomers of resveratrol will facilitate the biological studies necessary to elucidate their mechanism(s) of action. PMID:27940867

  7. Total Synthesis of (±)-Cis-Trikentrin B via Intermolecular 6,7-Indole Aryne Cycloaddition and Stille Cross-Coupling.

    PubMed

    Chandrasoma, Nalin; Brown, Neil; Brassfield, Allen; Nerurkar, Alok; Suarez, Susana; Buszek, Keith R

    2013-02-20

    An efficient total synthesis of the annulated indole natural product (±)- cis -trikentrin B was accomplished by means of a regioselectively generated 6,7-indole aryne cycloaddition via selective metal-halogen exchange from a 5,6,7-tribromoindole. The unaffected C-5 bromine was subsequently used for a Stille cross-coupling to install the butenyl side chain and complete the synthesis. This strategy provides rapid access into the trikentrins and the related herbindoles, and represents another application of this methodology to natural products total synthesis. The required 5,6,7-indole aryne precursor was prepared using the Leimgruber-Batcho indole synthesis.

  8. Microwave promoted simple, efficient and regioselective synthesis of trisubstituted imidazo[1,2-a]benzimidazoles on soluble support.

    PubMed

    Chen, Li-Hsun; Hsiao, Ya-Shan; Yellol, Gorakh S; Sun, Chung-Ming

    2011-03-14

    An efficient microwave-assisted and soluble polymer-supported synthesis of medicinally important imidazole-fused benzimidazoles has been developed. The protocol involves the rapid condensation of polymer-bound amino benzimidazoles with various α-bromoketones and subsequent in situ intramolecular cyclization under microwave irradiation resulting in a one pot synthesis of imidazole interlacing benzimidazole polymer conjugates. The condensed product was obtained with excellent regioselectivity. The biologically interesting imidazo[1,2-a]benzimidazoles was released from polymer support at ambient temperature. Diversity in the triheterocyclic nucleus was achieved by the different substitutions at its 2, 3, and 9 positions. The new protocol has the advantages of short reaction time, easy workup process, excellent yields, reduced environmental impact, wide substrate scope and convenient procedure.

  9. Copper-catalyzed aerobic oxidative C-H functionalization of substituted pyridines: synthesis of imidazopyridine derivatives.

    PubMed

    Yu, Jipan; Jin, Yunhe; Zhang, Hao; Yang, Xiaobo; Fu, Hua

    2013-12-02

    A novel, efficient, and practical method for the synthesis of imidazopyridine derivatives has been developed through the copper-catalyzed aerobic oxidative C-H functionalization of substituted pyridines with N-(alkylidene)-4H-1,2,4-triazol-4-amines. The procedure occurs by cleavage of the N-N bond in the N-(alkylidene)-4H-1,2,4-triazol-4-amines and activation of an aryl C-H bond in the substituted pyridines. This is the first example of the preparation of imidazopyridine derivatives by using pyridines as the substrates by transition-metal-catalyzed C-H functionalization. This method should provide a novel and efficient strategy for the synthesis of other nitrogen heterocycles. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Energy efficiency in nanoscale synthesis using nanosecond plasmas

    PubMed Central

    Pai, David Z.; (Ken) Ostrikov, Kostya; Kumar, Shailesh; Lacoste, Deanna A.; Levchenko, Igor; Laux, Christophe O.

    2013-01-01

    We report a nanoscale synthesis technique using nanosecond-duration plasma discharges. Voltage pulses 12.5 kV in amplitude and 40 ns in duration were applied repetitively at 30 kHz across molybdenum electrodes in open ambient air, generating a nanosecond spark discharge that synthesized well-defined MoO3 nanoscale architectures (i.e. flakes, dots, walls, porous networks) upon polyamide and copper substrates. No nitrides were formed. The energy cost was as low as 75 eV per atom incorporated into a nanostructure, suggesting a dramatic reduction compared to other techniques using atmospheric pressure plasmas. These findings show that highly efficient synthesis at atmospheric pressure without catalysts or external substrate heating can be achieved in a simple fashion using nanosecond discharges. PMID:23386976

  11. Thermodynamic and achievable efficiencies for solar-driven electrochemical reduction of carbon dioxide to transportation fuels

    PubMed Central

    Singh, Meenesh R.; Clark, Ezra L.; Bell, Alexis T.

    2015-01-01

    Thermodynamic, achievable, and realistic efficiency limits of solar-driven electrochemical conversion of water and carbon dioxide to fuels are investigated as functions of light-absorber composition and configuration, and catalyst composition. The maximum thermodynamic efficiency at 1-sun illumination for adiabatic electrochemical synthesis of various solar fuels is in the range of 32–42%. Single-, double-, and triple-junction light absorbers are found to be optimal for electrochemical load ranges of 0–0.9 V, 0.9–1.95 V, and 1.95–3.5 V, respectively. Achievable solar-to-fuel (STF) efficiencies are determined using ideal double- and triple-junction light absorbers and the electrochemical load curves for CO2 reduction on silver and copper cathodes, and water oxidation kinetics over iridium oxide. The maximum achievable STF efficiencies for synthesis gas (H2 and CO) and Hythane (H2 and CH4) are 18.4% and 20.3%, respectively. Whereas the realistic STF efficiency of photoelectrochemical cells (PECs) can be as low as 0.8%, tandem PECs and photovoltaic (PV)-electrolyzers can operate at 7.2% under identical operating conditions. We show that the composition and energy content of solar fuels can also be adjusted by tuning the band-gaps of triple-junction light absorbers and/or the ratio of catalyst-to-PV area, and that the synthesis of liquid products and C2H4 have high profitability indices. PMID:26504215

  12. Thermodynamic and achievable efficiencies for solar-driven electrochemical reduction of carbon dioxide to transportation fuels

    DOE PAGES

    Singh, Meenesh R.; Clark, Ezra L.; Bell, Alexis T.

    2015-10-26

    Thermodynamic, achievable, and realistic efficiency limits of solar-driven electrochemical conversion of water and carbon dioxide to fuels are investigated as functions of light-absorber composition and configuration, and catalyst composition. The maximum thermodynamic efficiency at 1-sun illumination for adiabatic electrochemical synthesis of various solar fuels is in the range of 32–42%. Single-, double-, and triple-junction light absorbers are found to be optimal for electrochemical load ranges of 0–0.9 V, 0.9–1.95 V, and 1.95–3.5 V, respectively. Achievable solar-to-fuel (STF) efficiencies are determined using ideal double- and triple-junction light absorbers and the electrochemical load curves for CO 2 reduction on silver and coppermore » cathodes, and water oxidation kinetics over iridium oxide. The maximum achievable STF efficiencies for synthesis gas (H 2 and CO) and Hythane (H 2 and CH 4) are 18.4% and 20.3%, respectively. Whereas the realistic STF efficiency of photoelectrochemical cells (PECs) can be as low as 0.8%, tandem PECs and photovoltaic (PV)-electrolyzers can operate at 7.2% under identical operating conditions. Finally, we show that the composition and energy content of solar fuels can also be adjusted by tuning the band-gaps of triple-junction light absorbers and/or the ratio of catalyst-to-PV area, and that the synthesis of liquid products and C 2H 4 have high profitability indices.« less

  13. Facile synthesis of semi-library of low charge density cationic polyesters from poly(alkylene maleate)s for efficient local gene delivery.

    PubMed

    Yan, Huijie; Zhu, Dingcheng; Zhou, Zhuxian; Liu, Xin; Piao, Ying; Zhang, Zhen; Liu, Xiangrui; Tang, Jianbin; Shen, Youqing

    2018-03-30

    Cationic polymers are one of the main non-viral vectors for gene therapy, but their applications are hindered by the toxicity and inefficient transfection, particularly in the presence of serum or other biological fluids. While rational design based on the current understanding of gene delivery process has produced various cationic polymers with improved overall transfection, high-throughput parallel synthesis of libraries of cationic polymers seems a more effective strategy to screen out efficacious polymers. Herein, we demonstrate a novel platform for parallel synthesis of low cationic charge-density polyesters for efficient gene delivery. Unsaturated polyester poly(alkylene maleate) (PAM) readily underwent Michael-addition reactions with various mercaptamines to produce polyester backbones with pendant amine groups, poly(alkylene maleate mercaptamine)s (PAMAs). Variations of the alkylenes in the backbone and the mercaptamines on the side chain produced PAMAs with tunable hydrophobicity and DNA-condensation ability, the key parameters dominating transfection efficiency of the resulting polymer/DNA complexes (polyplexes). A semi-library of such PAMAs was exampled from 7 alkylenes and 18 mercaptamines, from which a lead PAMA, G-1, synthesized from poly(1,4-phenylene bis(methylene) maleate) and N,N-dimethylcysteamine, showed remarkable transfection efficiency even in the presence of serum, owing to its efficient lysosome-circumventing cellular uptake. Furthermore, G-1 polyplexes efficiently delivered the suicide gene pTRAIL to intraperitoneal tumors and elicited effective anticancer activity. Copyright © 2018 Elsevier Ltd. All rights reserved.

  14. Sequence and structure-specific elements of HERG mRNA determine channel synthesis and trafficking efficiency

    PubMed Central

    Sroubek, Jakub; Krishnan, Yamini; McDonald, Thomas V.

    2013-01-01

    Human ether-á-gogo-related gene (HERG) encodes a potassium channel that is highly susceptible to deleterious mutations resulting in susceptibility to fatal cardiac arrhythmias. Most mutations adversely affect HERG channel assembly and trafficking. Why the channel is so vulnerable to missense mutations is not well understood. Since nothing is known of how mRNA structural elements factor in channel processing, we synthesized a codon-modified HERG cDNA (HERG-CM) where the codons were synonymously changed to reduce GC content, secondary structure, and rare codon usage. HERG-CM produced typical IKr-like currents; however, channel synthesis and processing were markedly different. Translation efficiency was reduced for HERG-CM, as determined by heterologous expression, in vitro translation, and polysomal profiling. Trafficking efficiency to the cell surface was greatly enhanced, as assayed by immunofluorescence, subcellular fractionation, and surface labeling. Chimeras of HERG-NT/CM indicated that trafficking efficiency was largely dependent on 5′ sequences, while translation efficiency involved multiple areas. These results suggest that HERG translation and trafficking rates are independently governed by noncoding information in various regions of the mRNA molecule. Noncoding information embedded within the mRNA may play a role in the pathogenesis of hereditary arrhythmia syndromes and could provide an avenue for targeted therapeutics.—Sroubek, J., Krishnan, Y., McDonald, T V. Sequence- and structure-specific elements of HERG mRNA determine channel synthesis and trafficking efficiency. PMID:23608144

  15. Comparison of Full and Partial Admission Flow Fields in the Simplex Turbine

    NASA Technical Reports Server (NTRS)

    Dorney, Daniel J.; Griffin, Lisa W.; Sondak, Douglas L.

    2001-01-01

    The objectives of this project were to: (1) determine the effects of partial admission flow on rotor performance as a function of circumferential location and on unsteady rotor loading; and (2) Provide an efficient technique for determining turbine performance. Full admission simulation ws performed for the Simplex turbine and partial admission simulation is underway for the Simplex turbine.

  16. Synthesis and characterization of nanoparticles conjugated tannase and using it for enhancement of antibacterial activity of tannase produced by Serratia marcescens.

    PubMed

    Nsayef Muslim, D Sahira; Abbas Dham, Ziyad; J Mohammed, D Nadheer

    2017-09-01

    Fourteen isolates of Serratia marcescens were collected from patients suffering from septicemia. All theseisolates revealed different levels in tannase production. Tannase was partially purified from Serratia marcescens b9 by precipitation method at 70% saturation of ammonium sulfate. Au, Pt, SnO 2 and SiO 2 nanoparticles were prepared by laser ablation and examined by transmission electron microscopy (TEM), X-ray diffraction pattern and UV-Visible absorption spectroscopy. Conjugation of SiO 2 nanoparticles to tannase by feeding and pulses methods were prepared and characterized by TEM, X-ray diffraction pattern and UV-Visible spectrum. SiO 2 nanoparticles conjugated partially purified tannase by feeding showed the higher effectiveness and higher significant level against all tested UTI causing in comparison with ciprofloxacin antibiotic, SiO 2 nanoparticles alone, partially purified tannase alone and partially purified tannase by pulses. So that we can conclude that feeding method was the best method for enhancement partially purified tannase activity to maximum level thus SiO 2 nanoparticles conjugated partially purified tannase may be a useful antibacterial agent for the treatment of urinary tract infection. Copyright © 2017 Elsevier Ltd. All rights reserved.

  17. Gold nanoparticles supported on titanium dioxide: an efficient catalyst for highly selective synthesis of benzoxazoles and benzimidazoles.

    PubMed

    Tang, Lin; Guo, Xuefeng; Yang, Yu; Zha, Zhenggen; Wang, Zhiyong

    2014-06-11

    A highly efficient and selective reaction for the synthesis of 2-substituted benzoxazoles and benzimidazoles catalyzed by Au/TiO2 has been developed via two hydrogen-transfer processes. This reaction has a good tolerance to air and water, a wide substrate scope, and represents a new avenue for practical C-N and C-O bond formation. More importantly, no additional additives, oxidants and reductants are required for the reaction and the catalyst can be recovered and reused readily.

  18. An Efficient Synthesis of 2-Substituted Benzimidazoles via Photocatalytic Condensation of o-Phenylenediamines and Aldehydes.

    PubMed

    Kovvuri, Jeshma; Nagaraju, Burri; Kamal, Ahmed; Srivastava, Ajay K

    2016-10-10

    A photocatalytic method has been developed for the efficient synthesis of functionalized benzimidazoles. This protocol involves photocatalytic condensation of o-phenylenediamines with various aldehydes using the Rose Bengal as photocatalyst. The method was found to be general and was successfully employed for accessing pharmaceutically important benzimidazoles by the condensation of aromatic, heteroaromatic and aliphatic aldehydes with o-phenylenediamines, in good-to-excellent yields. Notably, the method was found to be effective for the condensation of less reactive heterocyclic aldehydes with o-phenylenediamines.

  19. New Efficient Synthesis of 3,4-Dihydropyrimidin-2(1H)-ones Catalyzed by Benzotriazolium-Based Ionic Liquids under Solvent-Free Conditions.

    PubMed

    Liu, Zhiqing; Ma, Rong; Cao, Dawei; Liu, Chenjiang

    2016-04-07

    An efficient synthesis of novel 3,4-dihydropyrimidin-2(1H)-ones (DHPMs) and their derivatives, using Brønsted acidic ionic liquid [C₂O₂BBTA][TFA] as a catalyst, from the condensation of aryl aldehyde, β-ketoester and urea was described. Reactions proceeded smoothly for 40 min under solvent-free conditions and gave the desirable products with good to excellent yields (up to 99%). The catalyst could be easily recycled and reused with similar efficacies for at least six cycles.

  20. Synthesis of a Monophosphoryl Derivative of Escherichia coli Lipid A and Its Efficient Coupling to a Tumor-Associated Carbohydrate Antigen

    PubMed Central

    Tang, Shouchu; Wang, Qianli

    2010-01-01

    Monophosphoryl lipid A is a safe and potent immunostimulant and vaccine adjuvant, which is potentially useful for the development of effective carbohydrate-based conjugate vaccines. This paper presented a convergent and efficient synthesis of a monophosphoryl derivative of E. coli lipid A having an alkyne functionality at the reducing end, which is suitable for the coupling with various molecules. The coupling of this derivative to an N-modified analog of tumor-associated antigen GM3 by click chemistry is also presented. PMID:19943286

  1. Low-temperature synthesis of allyl dimethylamine by selective heating under microwave irradiation used for water treatment

    NASA Astrophysics Data System (ADS)

    Tian, Binghui; Luan, Zhaokun; Li, Mingming

    2005-08-01

    Low-temperature synthesis of allyl dimethylamine (ADA) by selective heating under microwave irradiation (MI) used for water treatment is investigated. The effect of MI, ultrasound irradiation (UI) and conventional heating on yield of ADA, reaction time and the flocculation efficiency of polydiallyl dimethylammunion chloride (PDADMAC) prepared form ADA were studied. The results show that by selective heating at low temperature, MI not only increases yield of ADA and reduces reaction time, but also greatly enhances the flocculation efficiency of PDADMAC.

  2. Fabrication of highly efficient ZnO nanoscintillators

    NASA Astrophysics Data System (ADS)

    Procházková, Lenka; Gbur, Tomáš; Čuba, Václav; Jarý, Vítězslav; Nikl, Martin

    2015-09-01

    Photo-induced synthesis of high-efficiency ultrafast nanoparticle scintillators of ZnO was demonstrated. Controlled doping with Ga(III) and La(III) ions together with the optimized method of ZnO synthesis and subsequent two-step annealing in air and under reducing atmosphere allow to achieve very high intensity of UV exciton luminescence, up to 750% of BGO intensity magnitude. Fabricated nanoparticles feature extremely short sub-nanosecond photoluminescence decay times. Temperature dependence of the photoluminescence spectrum within 8-340 K range was investigated and shows the absence of visible defect-related emission within all temperature intervals.

  3. A highly efficient green synthesis of 1, 8-dioxo-octahydroxanthenes

    PubMed Central

    2011-01-01

    SmCl3 (20 mol%) has been used as an efficient catalyst for reaction between aromatic aldehydes and 5,5-dimethyl-1,3-cyclohexanedione at 120°C to give 1,8-dioxo-octahydroxanthene derivatives in high yield. The same reaction in water, at room temperature gave only the open chain analogue of 1,8-dioxo-octahydroxanthene. Use of eco-friendly green Lewis acid, readily available catalyst and easy isolation of the product makes this a convenient method for the synthesis of either of the products. PMID:22152051

  4. An essential role of the mitochondrial electron transport chain in cell proliferation is to enable aspartate synthesis

    PubMed Central

    Birsoy, Kıvanç; Wang, Tim; Chen, Walter; Freinkman, Elizaveta; Abu-Remaileh, Monther; Sabatini, David M.

    2015-01-01

    Summary The mitochondrial electron transport chain (ETC) enables many metabolic processes, but why its inhibition suppresses cell proliferation is unclear. It is also not well understood why pyruvate supplementation allows cells lacking ETC function to proliferate. We used a CRISPR-based genetic screen to identify genes whose loss sensitizes human cells to phenformin, a complex I inhibitor. The screen yielded GOT1, the cytosolic aspartate aminotransferase, loss of which kills cells upon ETC inhibition. GOT1 normally consumes aspartate to transfer electrons into mitochondria, but, upon ETC inhibition, it reverses to generate aspartate in the cytosol, which partially compensates for the loss of mitochondrial aspartate synthesis. Pyruvate stimulates aspartate synthesis in a GOT1-dependent fashion, which is required for pyruvate to rescue proliferation of cells with ETC dysfunction. Aspartate supplementation or overexpression of an aspartate transporter allows cells without ETC activity to proliferate. Thus, enabling aspartate synthesis is an essential role of the ETC in cell proliferation. PMID:26232224

  5. An Essential Role of the Mitochondrial Electron Transport Chain in Cell Proliferation Is to Enable Aspartate Synthesis.

    PubMed

    Birsoy, Kıvanç; Wang, Tim; Chen, Walter W; Freinkman, Elizaveta; Abu-Remaileh, Monther; Sabatini, David M

    2015-07-30

    The mitochondrial electron transport chain (ETC) enables many metabolic processes, but why its inhibition suppresses cell proliferation is unclear. It is also not well understood why pyruvate supplementation allows cells lacking ETC function to proliferate. We used a CRISPR-based genetic screen to identify genes whose loss sensitizes human cells to phenformin, a complex I inhibitor. The screen yielded GOT1, the cytosolic aspartate aminotransferase, loss of which kills cells upon ETC inhibition. GOT1 normally consumes aspartate to transfer electrons into mitochondria, but, upon ETC inhibition, it reverses to generate aspartate in the cytosol, which partially compensates for the loss of mitochondrial aspartate synthesis. Pyruvate stimulates aspartate synthesis in a GOT1-dependent fashion, which is required for pyruvate to rescue proliferation of cells with ETC dysfunction. Aspartate supplementation or overexpression of an aspartate transporter allows cells without ETC activity to proliferate. Thus, enabling aspartate synthesis is an essential role of the ETC in cell proliferation. Copyright © 2015 Elsevier Inc. All rights reserved.

  6. The effect of oxygen partial pressure on protein synthesis and collagen hydroxylation by mature periodontal tissues maintained in organ cultures

    PubMed Central

    Yen, Edwin H. K.; Sodek, Jaro; Melcher, Antony H.

    1979-01-01

    Mature periodontal tissues from adult-mouse first mandibular molars were cultured in a continuous-flow organ-culture system which allowed the regulation of both ascorbic acid concentration and pO2 (oxygen partial pressure). Protein synthesis was measured by analysing the incorporation of [3H]proline into collagenous and non-collagenous proteins during the last 24h of a 2-day culture. At low pO2 [16.0kPa (approx. 120mmHg)] approx. 60% of protein-incorporated [3H]proline was found in collagenous proteins. However, it was evident that this collagen was considerably underhydroxylated. At high pO2 [56.0kPa (approx. 420mmHg)], both the amount of collagen deposited in the tissues and the degree of hydroxylation were increased considerably. In contrast, no significant effect on non-collagenous protein was observed. Tissues cultured at low pO2 for the first 48h were unable to respond to a subsequent increase in pO2 during the last 24h. Analysis of pepsin-solubilized collagen α-chains labelled with [14C]glycine demonstrated the synthesis of both type-I and type-III collagens by explants cultured for 48h at high pO2. Type-III collagen comprised 20–30% of the radioactivity in α-chains in both the periodontal ligament and the tissues of the alveolar process. The pattern of protein synthesis in the alveolar tissues at high pO2 was similar to that observed in these tissues in vivo. However, in the cultured periodontal ligament the proportions of non-collagenous proteins and type-III collagens were increased in comparison with the tissue in vivo. PMID:454369

  7. Role of extracellular matrix in regulation of staurosporine-induced apoptosis in breast cancer cells.

    PubMed

    Vasaturo, F; Malacrino, C; Sallusti, E; Coppotelli, G; Birarelli, P; Giuffrida, A; Albonici, L; Simonelli, L; Modesti, A; Modesti, M; Scarpa, S

    2005-04-01

    Autocrine and paracrine mechanisms modulate the synthesis and secretion of extracellular matrix (ECM); moreover, each component of the ECM is capable of modulating the synthesis and release of other ECM molecules. Therefore, the synthesis of ECM glycoprotein fibronectin and laminin was studied in the human breast cancer cell lines MCF7 and MDA MB 23, plated on different ECM. Our results showed that the cells plated on a fibronectin substrate increased laminin synthesis: this event correlated with an increase in alpha2 and alpha3 integrin subunits. Staurosporine-induced apoptosis was then analyzed in the cell lines plated on different ECM. Staurosporine treatment determined the apoptosis of 35 and 33% respectively of MDA MB 231 and MCF7; these values increased to 60 and 64% in cells plated on laminin, to 48 and 63% in cells plated on fibronectin and to 64 and 69% in cells plated on matrigel. Moreover, staurosporine treatment decreased bcl-2 expression in the cells plated on fibronectin and laminin. Yet, staurosporine treatment determined PARP cleavage and PARP partial disappearance when the cells were plated on matrigel. Finally, a partial loss of function mutant Ras protein that activated only Raf pathway, was expressed in MCF7, in order to identify whether the increase of apoptosis induced by extracellular matrix involved the Raf/MAP kinase pathway. The increase of apoptosis of the cells plated on matrigel suggested that the activation of the Raf pathway is probably involved in the decrease of survival on matrigel. These data demonstrate that the modification of ECM modulates the apoptotic process of breast cancer cells and suggest that it is worthwhile to dissect the role of ECM in the control of apoptotic process.

  8. A model of binding on DNA microarrays: understanding the combined effect of probe synthesis failure, cross-hybridization, DNA fragmentation and other experimental details of affymetrix arrays

    PubMed Central

    2012-01-01

    Background DNA microarrays are used both for research and for diagnostics. In research, Affymetrix arrays are commonly used for genome wide association studies, resequencing, and for gene expression analysis. These arrays provide large amounts of data. This data is analyzed using statistical methods that quite often discard a large portion of the information. Most of the information that is lost comes from probes that systematically fail across chips and from batch effects. The aim of this study was to develop a comprehensive model for hybridization that predicts probe intensities for Affymetrix arrays and that could provide a basis for improved microarray analysis and probe development. The first part of the model calculates probe binding affinities to all the possible targets in the hybridization solution using the Langmuir isotherm. In the second part of the model we integrate details that are specific to each experiment and contribute to the differences between hybridization in solution and on the microarray. These details include fragmentation, wash stringency, temperature, salt concentration, and scanner settings. Furthermore, the model fits probe synthesis efficiency and target concentration parameters directly to the data. All the parameters used in the model have a well-established physical origin. Results For the 302 chips that were analyzed the mean correlation between expected and observed probe intensities was 0.701 with a range of 0.88 to 0.55. All available chips were included in the analysis regardless of the data quality. Our results show that batch effects arise from differences in probe synthesis, scanner settings, wash strength, and target fragmentation. We also show that probe synthesis efficiencies for different nucleotides are not uniform. Conclusions To date this is the most complete model for binding on microarrays. This is the first model that includes both probe synthesis efficiency and hybridization kinetics/cross-hybridization. These two factors are sequence dependent and have a large impact on probe intensity. The results presented here provide novel insight into the effect of probe synthesis errors on Affymetrix microarrays; furthermore, the algorithms developed in this work provide useful tools for the analysis of cross-hybridization, probe synthesis efficiency, fragmentation, wash stringency, temperature, and salt concentration on microarray intensities. PMID:23270536

  9. Partial admission effect on the performance and vibration of a supersonic impulse turbine

    NASA Astrophysics Data System (ADS)

    Lee, Hang Gi; Shin, Ju Hyun; Choi, Chang-Ho; Jeong, Eunhwan; Kwon, Sejin

    2018-04-01

    This study experimentally investigates the effects of partial admission on the performance and vibration outcomes of a supersonic impulse turbine with circular nozzles. The turbine of a turbopump for a gas-generator-type liquid rocket engine in the Korea Space Launch Vehicle-II is of the supersonic impulse type with the partial admission configuration for obtaining a high specific power. Partial admission turbines with a low-flow-rate working gas exhibit benefits over turbines with full admission, such as loss reduction, ease of controllability of the turbine power output, and simple turbine configurations with separate starting sections. However, the radial force of the turbine rotor due to the partial admission causes an increase in turbine vibration. Few experimental studies have previously been conducted regarding the partial admission effects on supersonic impulse turbines with circular nozzles. In the present study, performance tests of supersonic impulse turbines with circular nozzles were conducted for various partial admission ratios using a turbine test facility with high-pressure air in order to investigate the resulting aerodynamic performance and vibration. Four types of turbines with partial admission ratios of 0.17, 0.42, 0.75 and 0.83 were tested. Results show that the efficiencies at the design point increase linearly as the partial admission ratios increase. Moreover, as the velocity ratios increase, the difference in efficiency from the reference turbine with a partial admission ratio of 0.83 becomes increasingly significant, and the magnitudes of these differences are proportional to the square of the velocity ratios. Likewise, the decrease in the partial admission ratio results in an increase in the turbine vibration level owing to the increase in the radial force.

  10. Nafion®-catalyzed microwave-assisted Ritter reaction: An atom-economic solvent-free synthesis of amides

    EPA Science Inventory

    An atom-economic solvent-free synthesis of amides by the Ritter reaction of alcohols and nitriles under microwave irradiation is reported. This green protocol is catalyzed by solid supported Nafion®NR50 with improved efficiency and reduced waste production.

  11. Multivariate Meta-Analysis Using Individual Participant Data

    ERIC Educational Resources Information Center

    Riley, R. D.; Price, M. J.; Jackson, D.; Wardle, M.; Gueyffier, F.; Wang, J.; Staessen, J. A.; White, I. R.

    2015-01-01

    When combining results across related studies, a multivariate meta-analysis allows the joint synthesis of correlated effect estimates from multiple outcomes. Joint synthesis can improve efficiency over separate univariate syntheses, may reduce selective outcome reporting biases, and enables joint inferences across the outcomes. A common issue is…

  12. REVISITING CLASSICAL NUCLEOPHILIC SUBSTITUTIONS IN AQUEOUS MEDIUM: MICROWAVE-ASSISTED SYNTHESIS OF ALKYL AZIDES

    EPA Science Inventory

    An efficient and clean synthesis of alkyl azides using microwave (MW) radiation is described in aqueous medium by reacting alkyl halides or tosylates with alkali azides. This general and expeditious MW-enhanced approach to nucleophilic substitution reactions is applicable to the ...

  13. Total synthesis of a CD-ring: side-chain building block for preparing 17-epi-calcitriol derivatives from the Hajos-Parrish dione.

    PubMed

    Michalak, Karol; Wicha, Jerzy

    2011-08-19

    An efficient synthesis of the key building block for 17-epi-calctriol from the Hajos-Parrish dione involving a sequence of diastereoselective transformation of the azulene core and the side-chain construction is presented.

  14. Tag-KEM from Set Partial Domain One-Way Permutations

    NASA Astrophysics Data System (ADS)

    Abe, Masayuki; Cui, Yang; Imai, Hideki; Kurosawa, Kaoru

    Recently a framework called Tag-KEM/DEM was introduced to construct efficient hybrid encryption schemes. Although it is known that generic encode-then-encrypt construction of chosen ciphertext secure public-key encryption also applies to secure Tag-KEM construction and some known encoding method like OAEP can be used for this purpose, it is worth pursuing more efficient encoding method dedicated for Tag-KEM construction. This paper proposes an encoding method that yields efficient Tag-KEM schemes when combined with set partial one-way permutations such as RSA and Rabin's encryption scheme. To our knowledge, this leads to the most practical hybrid encryption scheme of this type. We also present an efficient Tag-KEM which is CCA-secure under general factoring assumption rather than Blum factoring assumption.

  15. Flow “Fine” Synthesis: High Yielding and Selective Organic Synthesis by Flow Methods

    PubMed Central

    2015-01-01

    Abstract The concept of flow “fine” synthesis, that is, high yielding and selective organic synthesis by flow methods, is described. Some examples of flow “fine” synthesis of natural products and APIs are discussed. Flow methods have several advantages over batch methods in terms of environmental compatibility, efficiency, and safety. However, synthesis by flow methods is more difficult than synthesis by batch methods. Indeed, it has been considered that synthesis by flow methods can be applicable for the production of simple gasses but that it is difficult to apply to the synthesis of complex molecules such as natural products and APIs. Therefore, organic synthesis of such complex molecules has been conducted by batch methods. On the other hand, syntheses and reactions that attain high yields and high selectivities by flow methods are increasingly reported. Flow methods are leading candidates for the next generation of manufacturing methods that can mitigate environmental concerns toward sustainable society. PMID:26337828

  16. Synthetic versatility of 2-substituted-6-methyl 2,3-dihydropyridinones in the synthesis of polyfunctional piperidine-based compounds and related β amino acid derivatives.

    PubMed

    Yang, Yang; Hardman, Clayton

    2017-10-18

    Chiral 2-substituted-6-methyl 2,3-dihydropyidinones 9, which can be facilely obtained from an asymmetric vinylogous Mannich reaction (VMR) with 1,3-bis-trimethysily enol ether, were used as versatile intermediates in constructing chiral polyfunctional piperidine-based compounds. The 6-methyl group of such compounds can be conveniently functionalized via alkylation and acylation reactions to provide efficient entries to the synthesis of a variety of chiral multi-substituted piperidine-based compounds. Further elaboration of the corresponding intermediates also provided access to polyfunctional indolizidine-based compounds. These methods were showcased in an asymmetric synthesis of 2,6-di-substituted piperidine compound 13, reported as the key intermediate in the synthesis of (+)-calvine and a natural alkaloid (-)-indolizidine 209D. Furthermore, selective C5 iodination of compound 9 enabled the installation of additional functional groups at this position. Finally, we demonstrated that the oxidative cleavage of 2-substituted-6-methyl-2,3-dihydropyidinones is a practical and efficient method for the enantioselective synthesis of β-amino acids, which can undergo further intra-molecular cyclization to give the corresponding chiral four-membered β-lactam derivatives.

  17. Computerized Design Synthesis (CDS), A database-driven multidisciplinary design tool

    NASA Technical Reports Server (NTRS)

    Anderson, D. M.; Bolukbasi, A. O.

    1989-01-01

    The Computerized Design Synthesis (CDS) system under development at McDonnell Douglas Helicopter Company (MDHC) is targeted to make revolutionary improvements in both response time and resource efficiency in the conceptual and preliminary design of rotorcraft systems. It makes the accumulated design database and supporting technology analysis results readily available to designers and analysts of technology, systems, and production, and makes powerful design synthesis software available in a user friendly format.

  18. Combustion and Plasma Synthesis of High Temperature Materials

    DTIC Science & Technology

    1989-10-01

    photodetectors were constructed having tin oxide electrodes deposited under more and less severe condi- tions. The relative quantum efficiencies of these de ...PROPAGATING REACTION PROCESS 19 N. Sata, N. Sanada, T. Hirano, and M. Nilno COMBUSTION SYNTHESIS OF OXIDE -CARBIDE COMPOSITES L. L. Wang, Z. A. Munir, and J...SYNTHESIS OF CERAMIC POWDERS J. S. McFeaters and J. J. Moore 46 DEVELOPMENT OF TIN OXIDE COATINGS FOR USE AS ELECTRODES IN MERCURIC IODIDE

  19. Dearomatization Strategies in the Synthesis of Complex Natural Products

    PubMed Central

    Roche, Stéphane P.; Porco, John A.

    2014-01-01

    Evolution in the field of the total synthesis of natural products has led to exciting developments over the last decade. Numerous chemo-selective and enantioselective methodologies have emerged from total syntheses, resulting in efficient access to many important natural product targets. This Review highlights recent developments concerning dearomatization, a powerful strategy for the total synthesis of architecturally complex natural products wherein planar, aromatic scaffolds are converted to three-dimensional molecular architectures. PMID:21506209

  20. Convenient divergent strategy for the synthesis of TunePhos-type chiral diphosphine ligands and their applications in highly enantioselective Ru-catalyzed hydrogenations.

    PubMed

    Sun, Xianfeng; Zhou, Le; Li, Wei; Zhang, Xumu

    2008-02-01

    A convenient, divergent strategy for the synthesis of a series of modular and fine-tunable C3-TunePhos-type chiral diphosphine ligands and their applications in highly efficient Ru-catalyzed asymmetric hydrogenations were explored. Up to 97 and 99% ee values were achieved for the enantioselective synthesis of beta-methyl chiral amines and alpha-hydroxy acid derivatives, respectively.

  1. Combinatorial Partial Hydrogenation Reactions of 4-Nitroacetophenone: An Undergraduate Organic Laboratory

    ERIC Educational Resources Information Center

    Kittredge, Kevin W.; Marine, Susan S.; Taylor, Richard T.

    2004-01-01

    A molecule possessing other functional groups that could be hydrogenerated is examined, where a variety of metal catalysts are evaluated under similar reaction conditions. Optimizing organic reactions is both time and labor intensive, and the use of a combinatorial parallel synthesis reactor was great time saving device, as per summary.

  2. Generation of longitudinal vibrations in piano strings: From physics to sound synthesis

    NASA Astrophysics Data System (ADS)

    Bank, Balázs; Sujbert, László

    2005-04-01

    Longitudinal vibration of piano strings greatly contributes to the distinctive character of low piano notes. In this paper a simplified modal model is developed, which describes the generation of phantom partials and longitudinal free modes jointly. The model is based on the simplification that the coupling from the transverse vibration to the longitudinal polarization is unidirectional. The modal formulation makes it possible to predict the prominent components of longitudinal vibration as a function of transverse modal frequencies. This provides a qualitative insight into the generation of longitudinal vibration, while the model is still capable of explaining the empirical results of earlier works. The semi-quantitative agreement with measurement results implies that the main source of phantom partials is the transverse to longitudinal coupling, while the string termination and the longitudinal to transverse coupling have only small influence. The results suggest that the longitudinal component of the tone can be treated as a quasi-harmonic spectrum with formantlike peaks at the longitudinal modal frequencies. The model is further simplified and applied for the real-time synthesis of piano sound with convincing sonic results. .

  3. A synthesis theory for self-oscillating adaptive systems /SOAS/

    NASA Technical Reports Server (NTRS)

    Horowitz, I.; Smay, J.; Shapiro, A.

    1974-01-01

    A quantitative synthesis theory is presented for the Self-Oscillating Adaptive System (SOAS), whose nonlinear element has a static, odd character with hard saturation. The synthesis theory is based upon the quasilinear properties of the SOAS to forced inputs, which permits the extension of quantitative linear feedback theory to the SOAS. A reasonable definition of optimum design is shown to be the minimization of the limit cycle frequency. The great advantages of the SOAS is its zero sensitivity to pure gain changes. However, quasilinearity and control of the limit cycle amplitude at the system output, impose additional constraints which partially or completely cancel this advantage, depending on the numerical values of the design parameters. By means of narrow-band filtering, an additional factor is introduced which permits trade-off between filter complexity and limit cycle frequency minimization.

  4. Partial DNA-guided Cas9 enables genome editing with reduced off-target activity

    PubMed Central

    Yin, Hao; Song, Chun-Qing; Suresh, Sneha; Kwan, Suet-Yan; Wu, Qiongqiong; Walsh, Stephen; Ding, Junmei; Bogorad, Roman L; Zhu, Lihua Julie; Wolfe, Scot A; Koteliansky, Victor; Xue, Wen; Langer, Robert; Anderson, Daniel G

    2018-01-01

    CRISPR–Cas9 is a versatile RNA-guided genome editing tool. Here we demonstrate that partial replacement of RNA nucleotides with DNA nucleotides in CRISPR RNA (crRNA) enables efficient gene editing in human cells. This strategy of partial DNA replacement retains on-target activity when used with both crRNA and sgRNA, as well as with multiple guide sequences. Partial DNA replacement also works for crRNA of Cpf1, another CRISPR system. We find that partial DNA replacement in the guide sequence significantly reduces off-target genome editing through focused analysis of off-target cleavage, measurement of mismatch tolerance and genome-wide profiling of off-target sites. Using the structure of the Cas9–sgRNA complex as a guide, the majority of the 3′ end of crRNA can be replaced with DNA nucleotide, and the 5 - and 3′-DNA-replaced crRNA enables efficient genome editing. Cas9 guided by a DNA–RNA chimera may provide a generalized strategy to reduce both the cost and the off-target genome editing in human cells. PMID:29377001

  5. Subsurface synthesis and characterization of Ag nanoparticles embedded in MgO

    NASA Astrophysics Data System (ADS)

    Vilayurganapathy, S.; Devaraj, A.; Colby, R.; Pandey, A.; Varga, T.; Shutthanandan, V.; Manandhar, S.; El-Khoury, P. Z.; Kayani, Asghar; Hess, W. P.; Thevuthasan, S.

    2013-03-01

    Metal nanoparticles exhibit a localized surface plasmon resonance (LSPR) which is very sensitive to the size and shape of the nanoparticle and the surrounding dielectric medium. The coupling between the electromagnetic radiation and the localized surface plasmon in metallic nanoparticles results in a sizable enhancement of the incident fields, making them possible candidates for plasmonic applications. In particular, partially exposed metallic nanoparticles distributed in a dielectric matrix can provide prime locations for LSPR spectroscopy and sensing. We report the synthesis and characterization of a plasmonic substrate consisting of Ag nanoparticles partially buried in MgO. Ag nanoparticles of different shapes and size distributions were synthesized below the surface of MgO by implanting 200 keV Ag+ ions followed by annealing at 1000 °C for 10 and 30 h. A detailed optical and structural characterization was carried out to understand the evolution of the Ag nanoparticle and size distribution inside the MgO matrix. Micro x-ray diffraction (Micro-XRD) was employed to investigate the structural properties and estimate the crystallite size. The nanoparticles evolved from a spherical to a faceted morphology with annealing time, assuming an octahedral shape truncated at the (001) planes, as visualized from aberration-corrected transmission electron microscopy (TEM) images. The nanoparticles embedded in MgO were shown to be pure metallic Ag using atom probe tomography (APT). The nanoparticles were partially exposed to the surface by employing plasma etch techniques to remove the overlaying MgO. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) were employed to study the surface morphology and obtain a height distribution for the partially exposed nanoparticles.

  6. Synthesis and acid catalysis of cellulose-derived carbon-based solid acid

    NASA Astrophysics Data System (ADS)

    Suganuma, Satoshi; Nakajima, Kiyotaka; Kitano, Masaaki; Yamaguchi, Daizo; Kato, Hideki; Hayashi, Shigenobu; Hara, Michikazu

    2010-06-01

    SO 3H-bearing amorphous carbon, prepared by partial carbonization of cellulose followed by sulfonation in fuming H 2SO 4, was applied as a solid catalyst for the acid-catalyzed hydrolysis of β-1,4 glucan, including cellobiose and crystalline cellulose. Structural analyses revealed that the resulting carbon material consists of graphene sheets with 1.5 mmol g -1 of SO 3H groups, 0.4 mmol g -1 of COOH, and 5.6 mmol g -1 of phenolic OH groups. The carbon catalyst showed high catalytic activity for the hydrolysis of β-1,4 glycosidic bonds in both cellobiose and crystalline cellulose. Pure crystalline cellulose was not hydrolyzed by conventional strong solid Brønsted acid catalysts such as niobic acid, Nafion ® NR-50, and Amberlyst-15, whereas the carbon catalyst efficiently hydrolyzes cellulose into water-soluble saccharides. The catalytic performance of the carbon catalyst is due to the large adsorption capacity for hydrophilic reactants and the adsorption ability of β-1,4 glucan, which is not adsorbed to other solid acids.

  7. A Graphene-Based Biosensing Platform Based on Regulated Release of an Aptameric DNA Biosensor

    PubMed Central

    Mao, Yu; Chen, Yongli; Li, Song; Lin, Shuo; Jiang, Yuyang

    2015-01-01

    A novel biosensing platform was developed by integrating an aptamer-based DNA biosensor with graphene oxide (GO) for rapid and facile detection of adenosine triphosphate (ATP, as a model target). The DNA biosensor, which is locked by GO, is designed to contain two sensing modules that include recognition site for ATP and self-replication track that yields the nicking domain for Nt.BbvCI. By taking advantage of the different binding affinity of single-stranded DNA, double-stranded DNA and aptamer-target complex toward GO, the DNA biosensor could be efficiently released from GO in the presence of target with the help of a complementary DNA strand (CPDNA) that partially hybridizes to the DNA biosensor. Then, the polymerization/nicking enzyme synergetic isothermal amplification could be triggered, leading to the synthesis of massive DNA amplicons, thus achieving an enhanced sensitivity with a wide linear dynamic response range of four orders of magnitude and good selectivity. This biosensing strategy expands the applications of GO-DNA nanobiointerfaces in biological sensing, showing great potential in fundamental research and biomedical diagnosis. PMID:26569239

  8. A Graphene-Based Biosensing Platform Based on Regulated Release of an Aptameric DNA Biosensor.

    PubMed

    Mao, Yu; Chen, Yongli; Li, Song; Lin, Shuo; Jiang, Yuyang

    2015-11-09

    A novel biosensing platform was developed by integrating an aptamer-based DNA biosensor with graphene oxide (GO) for rapid and facile detection of adenosine triphosphate (ATP, as a model target). The DNA biosensor, which is locked by GO, is designed to contain two sensing modules that include recognition site for ATP and self-replication track that yields the nicking domain for Nt.BbvCI. By taking advantage of the different binding affinity of single-stranded DNA, double-stranded DNA and aptamer-target complex toward GO, the DNA biosensor could be efficiently released from GO in the presence of target with the help of a complementary DNA strand (CPDNA) that partially hybridizes to the DNA biosensor. Then, the polymerization/nicking enzyme synergetic isothermal amplification could be triggered, leading to the synthesis of massive DNA amplicons, thus achieving an enhanced sensitivity with a wide linear dynamic response range of four orders of magnitude and good selectivity. This biosensing strategy expands the applications of GO-DNA nanobiointerfaces in biological sensing, showing great potential in fundamental research and biomedical diagnosis.

  9. Amino acid substrates impose polyamine, eIF5A, or hypusine requirement for peptide synthesis

    PubMed Central

    Shin, Byung-Sik; Katoh, Takayuki; Gutierrez, Erik; Kim, Joo-Ran; Suga, Hiroaki

    2017-01-01

    Abstract Whereas ribosomes efficiently catalyze peptide bond synthesis by most amino acids, the imino acid proline is a poor substrate for protein synthesis. Previous studies have shown that the translation factor eIF5A and its bacterial ortholog EF-P bind in the E site of the ribosome where they contact the peptidyl-tRNA in the P site and play a critical role in promoting the synthesis of polyproline peptides. Using misacylated Pro-tRNAPhe and Phe-tRNAPro, we show that the imino acid proline and not tRNAPro imposes the primary eIF5A requirement for polyproline synthesis. Though most proline analogs require eIF5A for efficient peptide synthesis, azetidine-2-caboxylic acid, a more flexible four-membered ring derivative of proline, shows relaxed eIF5A dependency, indicating that the structural rigidity of proline might contribute to the requirement for eIF5A. Finally, we examine the interplay between eIF5A and polyamines in promoting translation elongation. We show that eIF5A can obviate the polyamine requirement for general translation elongation, and that this activity is independent of the conserved hypusine modification on eIF5A. Thus, we propose that the body of eIF5A functionally substitutes for polyamines to promote general protein synthesis and that the hypusine modification on eIF5A is critically important for poor substrates like proline. PMID:28637321

  10. Synthesis of public water supply use in the United States: Spatio-temporal patterns and socio-economic controls

    NASA Astrophysics Data System (ADS)

    Sankarasubramanian, A.; Sabo, J. L.; Larson, K. L.; Seo, S. B.; Sinha, T.; Bhowmik, R.; Vidal, A. Ruhi; Kunkel, K.; Mahinthakumar, G.; Berglund, E. Z.; Kominoski, J.

    2017-07-01

    Recent U.S. Geological Survey water-use report suggests that increasing water-use efficiency could mitigate the supply-and-demand imbalance arising from changing climate and growing population. However, this rich data have neither analyzed to understand the underlying patterns, nor have been investigated to identify the factors contributing to this increased efficiency. A national-scale synthesis of public supply withdrawals ("withdrawals") reveals a strong North-south gradient in public supply water use with the increasing population in the South contributing to increased withdrawal. Contrastingly, a reverse South-north gradient exists in per capita withdrawals ("efficiency"), with northern states consistently improving the efficiency, while the southern states' efficiency declined. Our analyses of spatial patterns of per capita withdrawals further demonstrate that urban counties exhibit improved efficiency over rural counties. Improved efficiency is also demonstrated over high-income and well-educated counties. Given the potential implications of the findings in developing long-term water conservation measures (i.e., increasing block rates), we argue the need for frequent updates, perhaps monthly to annual, of water-use data for identifying effective strategies that control the water-use efficiency in various geographic settings under a changing climate.

  11. Exploring the Fundamentals of Microreactor Technology with Multidisciplinary Lab Experiments Combining the Synthesis and Characterization of Inorganic Nanoparticles

    ERIC Educational Resources Information Center

    Emmanuel, Noemie; Emonds-Alt, Gauthier; Lismont, Marjorie; Eppe, Gauthier; Monbaliu, Jean-Christophe M.

    2017-01-01

    Multidisciplinary lab experiments combining microfluidics, nanoparticle synthesis, and characterization are presented. These experiments rely on the implementation of affordable yet efficient microfluidic setups based on perfluoroalkoxyalkane (PFA) capillary coils and standard HPLC connectors in upper undergraduate chemistry laboratories.…

  12. GREENER AND RAPID ACCESS TO BIO-ACTIVE HETEROCYCLES: ROOM TEMPERATURE SYNTHESIS OF PYRAZOLES AND DIAZEPINES IN AQUEOUS MEDIUM

    EPA Science Inventory

    An expeditious room temperature synthesis of pyrazoles and diazepines by condensation of hydrazines/hydrazides and diamines with various 1,3-diketones is described. This greener protocol was catalyzed by polystyrene supported sulfonic acid (PSSA) and proceeded efficiently in wate...

  13. An efficient and more sustainable one-step continuous-flow multicomponent synthesis approach to chromene derivatives

    EPA Science Inventory

    A simple and rapid one-step continuous-flow synthesis route has been developed for the preparation of chromene derivatives from the reaction of aromatic aldehydes, α-cyanomethylene compounds and naphthols. In this contribution, a one-step continuous-flow protocol in a continuous ...

  14. Improved Method for the Synthesis of β-Carbonyl Silyl-1,3-Dithianes by the Double Conjugate Addition of 1,3-Dithiol to Propargylic Carbonyl Compounds

    PubMed Central

    Mukherjee, Sumit; Kontokosta, Dimitra; Patil, Aditi; Rallapalli, Sivakumar; Lee, Daesung

    2009-01-01

    Base-mediated double conjugate addition of 1,3-propane dithiol to various silylated propargylic aldehydes and ketones allows for an efficient and scalable synthesis of β-carbonyl silyl-1,3-dithianes. PMID:19877611

  15. Nitric oxide-mediated suppression of 2,3-bisphosphoglycerate synthesis: therapeutic relevance for environmental hypoxia and sickle cell disease.

    PubMed

    Bertrand, R

    2012-09-01

    Though hemoglobin (Hb) is best known for transporting oxygen and metabolic wastes throughout the circulatory system, this erythrocyte protein also acts as a hypoxic sensor, its oxygen saturation dependent on the oxygen partial pressure (pO(2)) which varies throughout the vasculature. The production and transport of the endogenous vasodilator nitric oxide (NO) by Hb is dependent on Hb's oxygen saturation, thereby allowing the protein to auto-regulate blood flow efficiency to meet the relative demands of respiring tissues. Erythrocyte concentrations of 2,3-bisphosphoglycerate (BPG), an enhancer of oxygen off-loading from Hb, is very sensitive to changes in glycolytic rates because its synthesis by BPG synthase is dependent on the availability of the glycolytic intermediate 1,3-bisphosphoglycerate. BPG synthase, as well as some glycolytic enzymes, are also very sensitive to pH changes, and variations in BPG levels have direct consequences on the oxygen off-loading function of Hb. I hypothesize that NO may suppress BPG production by (1) inhibiting glyceraldehyde-3-phosphate dehydrogenase (G3PDH), the most critical glycolytic enzyme for the bioavailability of 1,3-bisphosphoglycerate; and to a lesser extent by (2) associated pH changes in the deoxy-Hb-catalyzed depletion of nitrite, a metabolic reservoir of NO. Both mechanisms are favored in low pO(2) environments where BPG is most needed to maximize oxygen off-loading, indicating that the auto-regulatory link between NO and Hb may have inadvertently linked Hb and BPG synthesis in an unfavorable manner. However, for reasons discussed, NO-mediated suppression of BPG may be advantageous in some circumstances; namely, for individuals living at high altitudes and those with the blood disorder sickle cell anemia. This hypothesis is thus relevant to respiratory health under both normative conditions as well as under hypoxic stress. The potential relevance of the hypothesis to comparative animal physiology and evolutionary biology is also briefly described. Copyright © 2012 Elsevier Ltd. All rights reserved.

  16. Design, Specification, and Synthesis of Aircraft Electric Power Systems Control Logic

    NASA Astrophysics Data System (ADS)

    Xu, Huan

    Cyber-physical systems integrate computation, networking, and physical processes. Substantial research challenges exist in the design and verification of such large-scale, distributed sensing, actuation, and control systems. Rapidly improving technology and recent advances in control theory, networked systems, and computer science give us the opportunity to drastically improve our approach to integrated flow of information and cooperative behavior. Current systems rely on text-based specifications and manual design. Using new technology advances, we can create easier, more efficient, and cheaper ways of developing these control systems. This thesis will focus on design considerations for system topologies, ways to formally and automatically specify requirements, and methods to synthesize reactive control protocols, all within the context of an aircraft electric power system as a representative application area. This thesis consists of three complementary parts: synthesis, specification, and design. The first section focuses on the synthesis of central and distributed reactive controllers for an aircraft elec- tric power system. This approach incorporates methodologies from computer science and control. The resulting controllers are correct by construction with respect to system requirements, which are formulated using the specification language of linear temporal logic (LTL). The second section addresses how to formally specify requirements and introduces a domain-specific language for electric power systems. A software tool automatically converts high-level requirements into LTL and synthesizes a controller. The final sections focus on design space exploration. A design methodology is proposed that uses mixed-integer linear programming to obtain candidate topologies, which are then used to synthesize controllers. The discrete-time control logic is then verified in real-time by two methods: hardware and simulation. Finally, the problem of partial observability and dynamic state estimation is explored. Given a set placement of sensors on an electric power system, measurements from these sensors can be used in conjunction with control logic to infer the state of the system.

  17. Impaired activity-dependent FMRP translation and enhanced mGluR-dependent LTD in Fragile X premutation mice

    PubMed Central

    Iliff, Adam J.; Renoux, Abigail J.; Krans, Amy; Usdin, Karen; Sutton, Michael A.; Todd, Peter K.

    2013-01-01

    Fragile X premutation-associated disorders, including Fragile X-associated Tremor Ataxia Syndrome, result from unmethylated CGG repeat expansions in the 5′ untranslated region (UTR) of the FMR1 gene. Premutation-sized repeats increase FMR1 transcription but impair rapid translation of the Fragile X mental retardation protein (FMRP), which is absent in Fragile X Syndrome (FXS). Normally, FMRP binds to RNA and regulates metabotropic glutamate receptor (mGluR)-mediated synaptic translation, allowing for dendritic synthesis of several proteins. FMRP itself is also synthesized at synapses in response to mGluR activation. However, the role of activity-dependent translation of FMRP in synaptic plasticity and Fragile X-premutation-associated disorders is unknown. To investigate this question, we utilized a CGG knock-in mouse model of the Fragile X premutation with 120–150 CGG repeats in the mouse Fmr1 5′ UTR. These mice exhibit increased Fmr1 mRNA production but impaired FMRP translational efficiency, leading to a modest reduction in basal FMRP expression. Cultured hippocampal neurons and synaptoneurosomes derived from CGG KI mice demonstrate impaired FMRP translation in response to the group I mGluR agonist 3,5-dihydroxyphenylglycine. Electrophysiological analysis reveals enhanced mGluR-mediated long-term depression (mGluR-LTD) at CA3–CA1 synapses in acute hippocampal slices prepared from CGG KI mice relative to wild-type littermates, similar to Fmr1 knockout mice. However, unlike mGluR-LTD in mice completely lacking FMRP, mGluR-LTD in CGG knock-in mice remains dependent on new protein synthesis. These studies demonstrate partially overlapping synaptic plasticity phenotypes in mouse models of FXS and Fragile X premutation disorders and support a role for activity-dependent synthesis of FMRP in enduring forms of synaptic plasticity. PMID:23250915

  18. Biocompatible PEGylated MoS2 nanosheets: controllable bottom-up synthesis and highly efficient photothermal regression of tumor.

    PubMed

    Wang, Shige; Li, Kai; Chen, Yu; Chen, Hangrong; Ma, Ming; Feng, Jingwei; Zhao, Qinghua; Shi, Jianlin

    2015-01-01

    Two-dimensional transition metal dichalcogenides, particularly MoS2 nanosheets, have been deemed as a novel category of NIR photothermal transducing agent. Herein, an efficient and versatile one-pot solvothermal synthesis based on "bottom-up" strategy has been, for the first time, proposed for the controlled synthesis of PEGylated MoS2 nanosheets by using a novel "integrated" precursor containing both Mo and S elements. This facile but unique PEG-mediated solvothermal procedure endowed MoS2 nanosheets with controlled size, increased crystallinity and excellent colloidal stability. The photothermal performance of nanosheets was optimized via modulating the particulate size and surface PEGylation. PEGylated MoS2 nanosheets with desired photothermal conversion performance and excellent colloidal and photothermal stability were further utilized for highly efficient photothermal therapy of cancer in a tumor-bearing mouse xenograft. Without showing observable in vitro and in vivo hemolysis, coagulation and toxicity, the optimized MoS2-PEG nanosheets showed promising in vitro and in vivo anti-cancer efficacy. Copyright © 2014 Elsevier Ltd. All rights reserved.

  19. An enhanced chemoenzymatic method for loading substrates onto carrier protein domains.

    PubMed

    Kittilä, Tiia; Cryle, Max J

    2018-06-01

    Non-ribosomal peptide synthetase (NRPS) machineries produce many medically relevant peptides that cannot be easily accessed by chemical synthesis. Thus, understanding NRPS mechanism is of crucial importance to allow efficient redesign of these machineries to produce new compounds. During NRPS-mediated synthesis, substrates are covalently attached to peptidyl carrier proteins (PCPs), and studies of NRPSs are impeded by difficulties in producing PCPs loaded with substrates. Different approaches to load substrates onto PCP domains have been described, but all suffer from difficulties in either the complexity of chemical synthesis or low enzymatic efficiency. Here, we describe an enhanced chemoenzymatic loading method that combines 2 approaches into a single, highly efficient one-pot loading reaction. First, d-pantetheine and ATP are converted into dephospho-coenzyme A via the actions of 2 enzymes from coenzyme A (CoA) biosynthesis. Next, phosphoadenylates are dephosphorylated using alkaline phosphatase to allow linker attachment to PCP domain by Sfp mutant R4-4, which is inhibited by phosphoadenylates. This route does not depend on activity of the commonly problematic dephospho-CoA kinase and, therefore, offers an improved method for substrate loading onto PCP domains.

  20. Synthesis of bis-Phosphate Iminoaltritol Enantiomers and Structural Characterization with Adenine Phosphoribosyltransferase.

    PubMed

    Harris, Lawrence D; Harijan, Rajesh K; Ducati, Rodrigo G; Evans, Gary B; Hirsch, Brett M; Schramm, Vern L

    2018-01-19

    Phosphoribosyl transferases (PRTs) are essential in nucleotide synthesis and salvage, amino acid, and vitamin synthesis. Transition state analysis of several PRTs has demonstrated ribocation-like transition states with a partial positive charge residing on the pentose ring. Core chemistry for synthesis of transition state analogues related to the 5-phospho-α-d-ribosyl 1-pyrophosphate (PRPP) reactant of these enzymes could be developed by stereospecific placement of bis-phosphate groups on an iminoaltritol ring. Cationic character is provided by the imino group and the bis-phosphates anchor both the 1- and 5-phosphate binding sites. We provide a facile synthetic path to these molecules. Cyclic-nitrone redox methodology was applied to the stereocontrolled synthesis of three stereoisomers of a selectively monoprotected diol relevant to the synthesis of transition-state analogue inhibitors. These polyhydroxylated pyrrolidine natural product analogues were bis-phosphorylated to generate analogues of the ribocationic form of 5-phosphoribosyl 1-phosphate. A safe, high yielding synthesis of the key intermediate represents a new route to these transition state mimics. An enantiomeric pair of iminoaltritol bis-phosphates (L-DIAB and D-DIAB) was prepared and shown to display inhibition of Plasmodium falciparum orotate phosphoribosyltransferase and Saccharomyces cerevisiae adenine phosphoribosyltransferase (ScAPRT). Crystallographic inhibitor binding analysis of L- and D-DIAB bound to the catalytic sites of ScAPRT demonstrates accommodation of both enantiomers by altered ring geometry and bis-phosphate catalytic site contacts.

  1. Reduced-order modelling of parameter-dependent, linear and nonlinear dynamic partial differential equation models.

    PubMed

    Shah, A A; Xing, W W; Triantafyllidis, V

    2017-04-01

    In this paper, we develop reduced-order models for dynamic, parameter-dependent, linear and nonlinear partial differential equations using proper orthogonal decomposition (POD). The main challenges are to accurately and efficiently approximate the POD bases for new parameter values and, in the case of nonlinear problems, to efficiently handle the nonlinear terms. We use a Bayesian nonlinear regression approach to learn the snapshots of the solutions and the nonlinearities for new parameter values. Computational efficiency is ensured by using manifold learning to perform the emulation in a low-dimensional space. The accuracy of the method is demonstrated on a linear and a nonlinear example, with comparisons with a global basis approach.

  2. Reduced-order modelling of parameter-dependent, linear and nonlinear dynamic partial differential equation models

    PubMed Central

    Xing, W. W.; Triantafyllidis, V.

    2017-01-01

    In this paper, we develop reduced-order models for dynamic, parameter-dependent, linear and nonlinear partial differential equations using proper orthogonal decomposition (POD). The main challenges are to accurately and efficiently approximate the POD bases for new parameter values and, in the case of nonlinear problems, to efficiently handle the nonlinear terms. We use a Bayesian nonlinear regression approach to learn the snapshots of the solutions and the nonlinearities for new parameter values. Computational efficiency is ensured by using manifold learning to perform the emulation in a low-dimensional space. The accuracy of the method is demonstrated on a linear and a nonlinear example, with comparisons with a global basis approach. PMID:28484327

  3. Erythrophagocytosis induces heat shock protein synthesis by human monocytes-macrophages.

    PubMed

    Clerget, M; Polla, B S

    1990-02-01

    Exposure of cells to elevated temperatures and other environmental stresses results in the expression of specific genes encoding the so-called heat shock proteins (HSPs). Since exogenous H2O2 induces in human monocytes the synthesis of HSPs, and previous induction of HSPs protects these cells from oxidative injury, we investigated whether HSP synthesis was also induced during generation of reactive oxygen species by the phagocyte itself during phagocytosis. As a model system, we analyzed the effects of erythrophagocytosis on protein synthesis by the human premonocytic line U937, in which phagocytosis is induced during differentiation with 1,25-dihydroxyvitamin D3. Exposure to whole erythrocytes, but not to erythrocyte ghosts, induced in the phagocytic cells only the synthesis of the 70- and 83- to 90-kDa HSPs and a 32-kDa oxidation-related stress protein identical by partial peptide mapping to heme oxygenase. The radioprotective aminothiol N-(2'-mercaptoethyl)-1,3-propanediamine (WR-1065), which can substitute for glutathione as hydrogen donor, prevented this induction. These results suggest that oxygen free radicals generated in the presence of hemoglobin-derived iron and consecutive glutathione depletion are involved in induction of stress protein synthesis during erythrophagocytosis. HSPs synthesized during phagocytosis may play a role in the phagocyte's defense mechanisms and in protective immunity.

  4. Assembly of Four Diverse Heterocyclic Libraries Enabled by Prins Cyclization, Au-Catalyzed Enyne Cycloisomerization, and Automated Amide Synthesis

    PubMed Central

    Cui, Jiayue; Chai, David I.; Miller, Christopher; Hao, Jason; Thomas, Christopher; Wang, JingQi; Scheidt, Karl A.; Kozmin, Sergey A.

    2013-01-01

    We describe a unified synthetic strategy for efficient assembly of four new heterocyclic libraries. The synthesis began by creating a range of structurally diverse pyrrolidinones or piperidinones. Such compounds were obtained in a simple one-flask operation starting with readily available amines, ketoesters, and unsaturated anhydrides. The use of tetrahydropyran-containing ketoesters, which were rapidly assembled by our Prins cyclization protocol, enabled efficient fusion of pyran and piperidinone cores. A newly developed Au(I)-catalyzed cycloisomerization of alkyne-containing enamides further expanded heterocyclic diversity by providing rapid entry into a wide range of bicyclic and tricyclic dienamides. The final stage of the process entailed diversification of each of the initially produced carboxylic acids using a fully automated platform for amide synthesis, which delivered 1872 compounds in high diastereomeric and chemical purity. PMID:22860634

  5. Optimality principle for the coupled chemical reactions of ATP synthesis and its molecular interpretation

    NASA Astrophysics Data System (ADS)

    Nath, Sunil

    2018-05-01

    Metabolic energy obtained from the coupled chemical reactions of oxidative phosphorylation (OX PHOS) is harnessed in the form of ATP by cells. We experimentally measured thermodynamic forces and fluxes during ATP synthesis, and calculated the thermodynamic efficiency, η and the rate of free energy dissipation, Φ. We show that the OX PHOS system is tuned such that the coupled nonequilibrium processes operate at optimal η. This state does not coincide with the state of minimum Φ but is compatible with maximum Φ under the imposed constraints. Conditions that must hold for species concentration in order to satisfy the principle of optimal efficiency are derived analytically and a molecular explanation based on Nath's torsional mechanism of energy transduction and ATP synthesis is suggested. Differences of the proposed principle with Prigogine's principle are discussed.

  6. Computer-oriented synthesis of wide-band non-uniform negative resistance amplifiers

    NASA Technical Reports Server (NTRS)

    Branner, G. R.; Chan, S.-P.

    1975-01-01

    This paper presents a synthesis procedure which provides design values for broad-band amplifiers using non-uniform negative resistance devices. Employing a weighted least squares optimization scheme, the technique, based on an extension of procedures for uniform negative resistance devices, is capable of providing designs for a variety of matching network topologies. It also provides, for the first time, quantitative results for predicting the effects of parameter element variations on overall amplifier performance. The technique is also unique in that it employs exact partial derivatives for optimization and sensitivity computation. In comparison with conventional procedures, significantly improved broad-band designs are shown to result.

  7. Analysis and synthesis of distributed-lumped-active networks by digital computer

    NASA Technical Reports Server (NTRS)

    1973-01-01

    The use of digital computational techniques in the analysis and synthesis of DLA (distributed lumped active) networks is considered. This class of networks consists of three distinct types of elements, namely, distributed elements (modeled by partial differential equations), lumped elements (modeled by algebraic relations and ordinary differential equations), and active elements (modeled by algebraic relations). Such a characterization is applicable to a broad class of circuits, especially including those usually referred to as linear integrated circuits, since the fabrication techniques for such circuits readily produce elements which may be modeled as distributed, as well as the more conventional lumped and active ones.

  8. Synthesis and degradation of nitrate reductase during the cell cycle of Chlorella sorokiniana

    NASA Technical Reports Server (NTRS)

    Velasco, P. J.; Tischner, R.; Huffaker, R. C.; Whitaker, J. R.

    1989-01-01

    Studies on the diurnal variations of nitrate reductase (NR) activity during the life cycle of synchronized Chlorella sorokiniana cells grown with a 7:5 light-dark cycle showed that the NADH:NR activity, as well as the NR partial activities NADH:cytochrome c reductase and reduced methyl viologen:NR, closely paralleled the appearance and disappearance of NR protein as shown by sodium dodecyl sulfate gel electrophoresis and immunoblots. Results of pulse-labeling experiments with [35S]methionine further confirmed that diurnal variations of the enzyme activities can be entirely accounted for by the concomitant synthesis and degradation of the NR protein.

  9. Design and Synthesis of Self-Assembled Monolayers on Mesoporous Supports (SAMMS): The Importance of Ligand Posture in Functional Nanomaterials

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

    Fryxell, Glen E.; Mattigod, Shas V.; Lin, Yuehe

    2007-07-01

    Water, and water quality, are issues of critical importance to the future of humankind. The Earth’s water supplies have been contaminated by a wide variety of industrial, military and natural sources. The need exists for an efficient separation technology to remove heavy metal and radionuclide contamination from water. Surfactant templated synthesis of mesoporous ceramics provides a versatile foundation upon which to build high efficiency environmental sorbents. These nanoporous ceramics condense a huge amount of surface area into a very small volume. These mesoporous architectures can be subsequently functionalized through molecular self-assembly. These functional mesoporous materials offer significant capabilities in termsmore » of removal of heavy metals and radionuclides from a variety of liquid media, including groundwater, contaminated oils and contaminated chemical weapons. They are highly efficient sorbents, whose rigid, open pore structure allows for rapid, efficient sorption kinetics. Their interfacial chemistry can be fine-tuned to selectively sequester a specific target species, such as heavy metals, tetrahedral oxometallate anions and radionuclides. This manuscript provides a review of the design, synthesis and performance of the sorbent materials. The role that ligand posture plays in the chemistry of these interfacial ligand fields is discussed.« less

  10. Diels-Alder and Stille Coupling Approach for the Short Protecting-Group-Free Synthesis of Mycophenolic Acid, Its Phenylsulfenyl and Phenylselenyl Analogues, and Reactive Oxygen Species (ROS) Probing Capacity in Water.

    PubMed

    Halle, Mahesh B; Yudhistira, Tesla; Lee, Woo-Hyun; Mulay, Sandip V; Churchill, David G

    2018-06-15

    A short, protecting-group-free synthesis is achieved. The synthesis is step-efficient and general. A Diels-Alder and Stille cross-coupling approach includes key transformations, allowing for a competitive synthesis which involves a rare halophenol Stille cross-coupling study. The phenylselenyl and phenylsulfenyl analogues were prepared as novel compounds in good overall yield. The applicability of one of the intermediates as a potential probe for reactive oxygen species (ROS) in water is investigated.

  11. Influence of Synthesis Mode of Supplement Based on Calcium Hydrosylicates on the Structure and Properties of Lime Compositions

    NASA Astrophysics Data System (ADS)

    Loganina, V. I.; Pyshkina, I. S.

    2017-11-01

    It was proposed to use synthesized calcium hydrosilicates in finishing lime dry mixes as a modifying supplement. The effect of substances containing amorphous silica which are used for synthesis on the activity of the modifying supplement was established. The effect of the synthesis mode of supplement on the structure formation of lime compositions was illustrated. It was found that the injection of supplements of hydrosilicates accelerates the increase of mechanical strength. The efficiency of the modifying supplements of amorphous silica, such as diatomite, in the synthesis was shown.

  12. Flow microreactor synthesis in organo-fluorine chemistry

    PubMed Central

    Nagaki, Aiichiro

    2013-01-01

    Summary Organo-fluorine compounds are the substances of considerable interest in various industrial fields due to their unique physical and chemical properties. Despite increased demand in wide fields of science, synthesis of fluoro-organic compounds is still often faced with problems such as the difficulties in handling of fluorinating reagents and in controlling of chemical reactions. Recently, flow microreactor synthesis has emerged as a new methodology for producing chemical substances with high efficiency. This review outlines the successful examples of synthesis and reactions of fluorine-containing molecules by the use of flow microreactor systems to overcome long-standing problems in fluorine chemistry. PMID:24367443

  13. Flow microreactor synthesis in organo-fluorine chemistry.

    PubMed

    Amii, Hideki; Nagaki, Aiichiro; Yoshida, Jun-Ichi

    2013-12-05

    Organo-fluorine compounds are the substances of considerable interest in various industrial fields due to their unique physical and chemical properties. Despite increased demand in wide fields of science, synthesis of fluoro-organic compounds is still often faced with problems such as the difficulties in handling of fluorinating reagents and in controlling of chemical reactions. Recently, flow microreactor synthesis has emerged as a new methodology for producing chemical substances with high efficiency. This review outlines the successful examples of synthesis and reactions of fluorine-containing molecules by the use of flow microreactor systems to overcome long-standing problems in fluorine chemistry.

  14. Stereoselective heterocycle synthesis through oxidative carbon-hydrogen bond activation.

    PubMed

    Liu, Lei; Floreancig, Paul E

    2010-01-01

    Heterocycles are ubiquitous structures in both drugs and natural products, and efficient methods for their construction are being pursued constantly. Carbon-hydrogen bond activation offers numerous advantages for the synthesis of heterocycles with respect to minimizing the length of synthetic routes and reducing waste. As interest in chiral medicinal leads increases, stereoselective methods for heterocycle synthesis must be developed. The use of carbon-hydrogen bond activation reactions for stereoselective heterocycle synthesis has produced a range of creative transformations that provide a wide array of structural motifs, selected examples of which are described in this review.

  15. Total synthesis of the cyclopeptide alkaloid abyssenine A. Application of inter- and intramolecular copper-mediated coupling reactions in organic synthesis.

    PubMed

    Toumi, Mathieu; Couty, François; Evano, Gwilherm

    2007-11-23

    The first total synthesis of the 15-membered ring cyclopeptide alkaloid abyssenine A 1 has been achieved with a longest linear sequence of 15 steps. Central to the synthetic approach was an efficient copper-mediated Ullmann coupling/Claisen rearrangement sequence allowing for both ipso and ortho functionalization of aromatic iodide 4. This sequence was used for the synthesis of the aromatic core. The synthetic utility of copper-catalyzed coupling reactions was further demonstrated to install the enamide with a concomitant straightforward macrocyclization starting from acyclic alpha-amido-omega-vinyl iodide 13.

  16. Thermolysis of Geminal Diazides: Reagent-Free Synthesis of 3-Hydroxypyridines.

    PubMed

    Erhardt, Hellmuth; Kunz, Kevin A; Kirsch, Stefan F

    2017-01-06

    An operationally simple protocol for the rapid and efficient construction of highly substituted 3-hydroxypyridines is presented. The thermally induced cyclization of easily constructed geminal diazides derived from β-ketoesters having an additional olefin moiety affords the title compounds in yields up to 97% under reagent-free conditions. The new method allows for the synthesis of preparative quantities of material. Additionally, the synthetic utility of the pyridine products for the synthesis of valuable heterocycles is described.

  17. Hyper-Acetylation of Histone H3K56 Limits Break-Induced Replication by Inhibiting Extensive Repair Synthesis

    PubMed Central

    Che, Jun; Smith, Stephanie; Kim, Yoo Jung; Shim, Eun Yong; Myung, Kyungjae; Lee, Sang Eun

    2015-01-01

    Break-induced replication (BIR) has been implicated in restoring eroded telomeres and collapsed replication forks via single-ended invasion and extensive DNA synthesis on the recipient chromosome. Unlike other recombination subtypes, DNA synthesis in BIR likely relies heavily on mechanisms enabling efficient fork progression such as chromatin modification. Herein we report that deletion of HST3 and HST4, two redundant de-acetylases of histone H3 Lysine 56 (H3K56), inhibits BIR, sensitizes checkpoint deficient cells to deoxyribonucleotide triphosphate pool depletion, and elevates translocation-type gross chromosomal rearrangements (GCR). The basis for deficiency in BIR and gene conversion with long gap synthesis in hst3Δ hst4Δ cells can be traced to a defect in extensive DNA synthesis. Distinct from other cellular defects associated with deletion of HST3 and HST4 including thermo-sensitivity and elevated spontaneous mutagenesis, the BIR defect in hst3Δ hst4Δ cannot be offset by the deletion of RAD17 or MMS22, but rather by the loss of RTT109 or ASF1, or in combination with the H3K56R mutation, which also restores tolerance to replication stress in mrc1 mutants. Our studies suggest that acetylation of H3K56 limits extensive repair synthesis and interferes with efficient fork progression in BIR. PMID:25705897

  18. Total synthesis of bryostatins: the development of methodology for the atom-economic and stereoselective synthesis of the ring C subunit.

    PubMed

    Trost, Barry M; Frontier, Alison J; Thiel, Oliver R; Yang, Hanbiao; Dong, Guangbin

    2011-08-22

    Bryostatins, a family of structurally complicated macrolides, exhibit an exceptional range of biological activities. The limited availability and structural complexity of these molecules makes development of an efficient total synthesis particularly important. This article describes our initial efforts towards the total synthesis of bryostatins, in which chemoselective and atom-economical methods for the stereoselective assembly of the ring C subunit were developed. A Pd-catalyzed tandem alkyne-alkyne coupling/6-endo-dig cyclization sequence was explored and successfully pursued in the synthesis of a dihydropyran ring system. Elaboration of this methodology ultimately led to a concise synthesis of the ring C subunit of bryostatins. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Opposite effects on regulation of urea synthesis by early and late uraemia in rats.

    PubMed

    Nielsen, Susanne Schouw; Grøfte, Thorbjørn; Grønbaek, Henning; Tygstrup, Niels; Vilstrup, Hendrik

    2007-04-01

    Acute and chronic kidney failure lead to catabolism with loss of lean body mass. Up-regulation of hepatic urea synthesis may play a role for the loss of body nitrogen and for the level of uraemia. The aims were to investigate the effects of early and late experimental renal failure on the regulation of hepatic urea synthesis and the expression of urea cycle enzyme genes in the liver. We examined the in vivo capacity of urea nitrogen synthesis, mRNA levels of urea cycle enzyme genes, and N-balances 6 days and 21 days after 5/6th partial nephrectomy in rats, and compared these data with pair- and free-fed control animals. Compared with pair-fed animals, early uraemia halved the in vivo urea synthesis capacity and decreased urea gene expressions (P<0.05). In contrast, late uraemia up-regulated in vivo urea synthesis and expression of all urea genes (P<0.05), save that of the flux-generating enzyme carbamoyl phosphate synthetase. The N-balance in rats with early uraemia was markedly negative (P<0.05) and near zero in late uraemia. Early uraemia down-regulated urea synthesis, so hepatic ureagenesis was not in itself involved in the negative N-balance. In contrast, late uraemia up-regulated urea synthesis, which probably contributed towards the reduced N-balance of this condition. These time-dependent, opposite effects on the uraemia-induced regulation of urea synthesis in vivo were not related to food restriction and probably mostly reflected regulation on gene level.

  20. Isolation and partial characterization of a mutant of Penicillium funiculosum for the saccharification of straw

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

    Hoffman, R.M.; Wood, T.M.

    1985-01-01

    Clearing of agar plates containing ball-milled, delignified straw has been used for screening mutants of Penicillium funiculosum IMI 87160 III. The effects of glycerol and a number of sugars on the clearing were investigated for selecting derepressed mutants. The ..beta..-glucosidase synthesis by one such mutant, C22c, in shake flasks containing straw was not repressed by 5% glycerol, whereas activities on filter paper, CM-cellulose, and p-nitrophenyl-..beta..-xylosidase were only partially derepressed; xylanase was extensively derepressed. The evidence for separate control of the enzymes involved in the solubilization of straw is discussed. 23 references.

  1. Persistent luminescence of transition metal (Co, Ni...)-doped ZnGa2O4 phosphors for applications in the near-infrared range

    NASA Astrophysics Data System (ADS)

    Pellerin, Morgane; Castaing, Victor; Gourier, Didier; Chanéac, Corinne; Viana, Bruno

    2018-02-01

    Persistent luminescence materials present many applications including security lighting and bio-imaging. Many progresses have been made in the elaboration of persistent luminescent nanoparticles suitable for the first NIR partial transparency window (650 - 950 nm). Moving to the second and third near-infrared partial transparency windows (1000 nm - 1800 nm) allows further reducing of scattering, absorption and tissue autofluorescence effects. In this work, we present the synthesis of Co2+ and Ni2+ doped zinc-gallate nanoparticles with broad emission covering the NIR-II range. Site occupancy, energy levels, optical features and persistent phenomena are presented.

  2. Big bang photosynthesis and pregalactic nucleosynthesis of light elements

    NASA Technical Reports Server (NTRS)

    Audouze, J.; Lindley, D.; Silk, J.

    1985-01-01

    Two nonstandard scenarios for pregalactic synthesis of the light elements (H-2, He-3, He-4, and Li-7) are developed. Big bang photosynthesis occurs if energetic photons, produced by the decay of massive neutrinos or gravitinos, partially photodisintegrate He-4 (formed in the standard hot big bang) to produce H-2 and He-3. In this case, primordial nucleosynthesis no longer constrains the baryon density of the universe, or the number of neutrino species. Alternatively, one may dispense partially or completely with the hot big bang and produce the light elements by bombardment of primordial gas, provided that He-4 is synthesized by a later generation of massive stars.

  3. Ultrasonic activated efficient synthesis of chromenes using amino-silane modified Fe3O4 nanoparticles: A versatile integration of high catalytic activity and facile recovery

    NASA Astrophysics Data System (ADS)

    Safari, Javad; Zarnegar, Zohre

    2014-08-01

    An efficient synthesis of 2-amino-4H-chromenes is achieved by one pot three component coupling reaction of aldehyde, malononitrile, and resorcinol using amino-silane modified Fe3O4 nanoparticles (MNPs-NH2) heterogeneous nanocatalyst under sonic condition. The attractive advantages of the present process are mild reaction conditions, short reaction times, easy isolation of products, good yields and simple operational procedures. Combination of the advantages of ultrasonic irradiation and magnetic nanoparticles provides important methodology to carry out catalytic transformations.

  4. Complete regioselective addition of grignard reagents to pyrazine N-oxides, toward an efficient enantioselective synthesis of substituted piperazines.

    PubMed

    Andersson, Hans; Banchelin, Thomas Sainte-Luce; Das, Sajal; Gustafsson, Magnus; Olsson, Roger; Almqvist, Fredrik

    2010-01-15

    A conceptually new one-pot strategy for the synthesis of protected substituted piperazines via the addition of Grignard reagents to pyrazine N-oxides is presented. This strategy is high yielding (33-91% over three steps), step-efficient, and fast. The synthesized N,N-diprotected piperazines are convenient to handle and allow for orthogonal deprotection at either nitrogen for selective transformations. In addition, this is a synthetic route to enantiomerically enriched piperazines by using a combination of phenyl magnesium chloride and (-)-sparteine, which resulted in enantiomeric excesses up to 83%.

  5. Studies towards asymmetric synthesis of 4(S)-11-dihydroxydocosahexaenoic acid (diHDHA) featuring cross-coupling of chiral stannane under mild conditions.

    PubMed

    Wang, Rui; He, Anyu; Ramu, Errabelli; Falck, John R

    2015-02-14

    An efficient and asymmetric synthetic approach towards one of the biologically interesting 4(S)-11-diHDHA derivatives was developed. This process mainly relied on two reactions, one is the copper-catalyzed mild cross-coupling that allows for the efficient construction of a chiral α-alkynyl α-hydroxy motif and another is the synthesis of chiral α-hydroxy α-stannanes that has previously been developed by our group featuring the asymmetric stannylation using the well-established tributyltin hydride/diethyl zinc system from an aldehyde.

  6. Inhibition of protein synthesis by N-methyl-N-nitrosourea in vivo

    PubMed Central

    Kleihues, P.; Magee, P. N.

    1973-01-01

    1. The intraperitoneal injection of N-methyl-N-nitrosourea (100mg/kg) caused a partial inhibition of protein synthesis in several organs of the rat, the maximum effect occurring after 2–3h. 2. In the liver the inhibition of protein synthesis was paralleled by a marked disaggregation of polyribosomes and an increase in ribosome monomers and ribosomal subunits. No significant breakdown of polyribosomes was found in adult rat brains although N-methyl-N-nitrosourea inhibited cerebral and hepatic protein synthesis to a similar extent. In weanling rats N-methyl-N-nitrosourea caused a shift in the cerebral polyribosome profile similar to but less marked than that in rat liver. 3. Reaction of polyribosomal RNA with N-[14C]methyl-N-nitrosourea in vitro did not lead to a disaggregation of polyribosomes although the amounts of 7-methylguanine produced were up to twenty times higher than those found after administration of sublethal doses in vivo. 4. It was concluded that changes in the polyribosome profile induced by N-methyl-N-nitrosourea may reflect the mechanism of inhibition of protein synthesis rather than being a direct consequence of the methylation of polyribosomal mRNA. PMID:4774397

  7. Increased de novo ceramide synthesis and accumulation in failing myocardium

    PubMed Central

    Ji, Ruiping; Akashi, Hirokazu; Drosatos, Konstantinos; Liao, Xianghai; Jiang, Hongfeng; Kennel, Peter J.; Brunjes, Danielle L.; Castillero, Estibaliz; Zhang, Xiaokan; Deng, Lily Y.; Homma, Shunichi; George, Isaac J.; Takayama, Hiroo; Naka, Yoshifumi; Goldberg, Ira J.

    2017-01-01

    Abnormal lipid metabolism may contribute to myocardial injury and remodeling. To determine whether accumulation of very long–chain ceramides occurs in human failing myocardium, we analyzed myocardial tissue and serum from patients with severe heart failure (HF) undergoing placement of left ventricular assist devices and controls. Lipidomic analysis revealed increased total and very long–chain ceramides in myocardium and serum of patients with advanced HF. After unloading, these changes showed partial reversibility. Following myocardial infarction (MI), serine palmitoyl transferase (SPT), the rate-limiting enzyme of the de novo pathway of ceramide synthesis, and ceramides were found increased. Blockade of SPT by the specific inhibitor myriocin reduced ceramide accumulation in ischemic cardiomyopathy and decreased C16, C24:1, and C24 ceramides. SPT inhibition also reduced ventricular remodeling, fibrosis, and macrophage content following MI. Further, genetic deletion of the SPTLC2 gene preserved cardiac function following MI. Finally, in vitro studies revealed that changes in ceramide synthesis are linked to hypoxia and inflammation. In conclusion, cardiac ceramides accumulate in the failing myocardium, and increased levels are detectable in circulation. Inhibition of de novo ceramide synthesis reduces cardiac remodeling. Thus, increased de novo ceramide synthesis contributes to progressive pathologic cardiac remodeling and dysfunction. PMID:28469091

  8. Activation of Cyclic AMP Synthesis by Full and Partial Beta-Adrenergic Receptor Agonists in Chicken Skeletal Muscle Cells

    NASA Technical Reports Server (NTRS)

    Young, R. B.; Bridge, K. Y.

    2003-01-01

    Several beta-adrenergic receptor (bAR) agonists are known to cause hypertrophy of skeletal muscle tissue. Accordingly, five bAR agonists encompassing a range in activity from strong to weak were evaluated for their ability to stimulate CAMP accumulation in embryonic chicken skeletal muscle cells in culture. Two strong agonists (epinephrine and isoproterenol), one moderate agonist (albuterol), and two weak agonists known to cause hypertrophy in animals (clenbuterol and cimaterol) were studied. Dose response curves were determined over six orders of magnitude in concentration for each agonist, and values were determined for their maximum stimulation of CAMP synthesis rate (Bmax) and the agonist concentration at which 50% stimulation of CAMP synthesis (EC50) occurred. Bmax values decreased in the following order: isoproterenol, epinephrine, albuterol, cimaterol, clenbuterol. Cimaterol and clenbuterol at their Bmax concentrations were approximately 15-fold weaker than isoproterenol in stimulating the rate of CAMP synthesis. When cimaterol and clenbuterol were added to culture media at concentrations known to cause significant muscle hypertrophy in animals, there was no detectable effect on stimulation of CAMP synthesis. Finally, these same levels of cimaterol and clenbuterol did not antagonize the stimulation of CAMP by either epinephrine or isoproterenol.

  9. Knowing the future: partial foreknowledge effects on the programming of prosaccades and antisaccades.

    PubMed

    Abegg, Mathias; Manoach, Dara S; Barton, Jason J S

    2011-01-01

    Foreknowledge about the demands of an upcoming trial may be exploited to optimize behavioural responses. In the current study we systematically investigated the benefits of partial foreknowledge--that is, when some but not all aspects of a future trial are known in advance. For this we used an ocular motor paradigm with horizontal prosaccades and antisaccades. Predictable sequences were used to create three partial foreknowledge conditions: one with foreknowledge about the stimulus location only, one with foreknowledge about the task set only, and one with foreknowledge about the direction of the required response only. These were contrasted with a condition of no-foreknowledge and a condition of complete foreknowledge about all three parameters. The results showed that the three types of foreknowledge affected saccadic efficiency differently. While foreknowledge about stimulus-location had no effect on efficiency, task foreknowledge had some effect and response-foreknowledge was as effective as complete foreknowledge. Foreknowledge effects on switch costs followed a similar pattern in general, but were not specific for switching of the trial attribute for which foreknowledge was available. We conclude that partial foreknowledge has a differential effect on efficiency, most consistent with preparatory activation of a motor schema in advance of the stimulus, with consequent benefits for both switched and repeated trials. Copyright © 2010 Elsevier Ltd. All rights reserved.

  10. Improving Qubit Phase Estimation in Amplitude-damping Channel by Partial-collapse Measurement

    NASA Astrophysics Data System (ADS)

    Liao, Xiang-Ping; Zhou, Xin; Fang, Mao-Fa

    2018-03-01

    An efficient method is proposed to improve qubit phase estimation in amplitude-damping channel by partial-collapse measurement in this paper. It is shown that the quantum Fisher information (QFI) can be distinctly enhanced under amplitude-damping decoherence with partial-collapse measurement. Moreover, the optimal QFI is approximately close to the maximum value 1 regardless of the decoherence parameter by choosing the appropriate measurement strengths.

  11. On the Solution of Elliptic Partial Differential Equations on Regions with Corners

    DTIC Science & Technology

    2015-07-09

    In this report we investigate the solution of boundary value problems on polygonal domains for elliptic partial differential equations . We observe...that when the problems are formulated as the boundary integral equations of classical potential theory, the solutions are representable by series of...efficient numerical algorithms. The results are illustrated by a number of numerical examples. On the solution of elliptic partial differential equations on

  12. The glycerol backbone of phospholipids derives from noncarbohydrate precursors in starved lung cancer cells.

    PubMed

    Leithner, Katharina; Triebl, Alexander; Trötzmüller, Martin; Hinteregger, Barbara; Leko, Petra; Wieser, Beatrix I; Grasmann, Gabriele; Bertsch, Alexandra L; Züllig, Thomas; Stacher, Elvira; Valli, Alessandro; Prassl, Ruth; Olschewski, Andrea; Harris, Adrian L; Köfeler, Harald C; Olschewski, Horst; Hrzenjak, Andelko

    2018-06-12

    Cancer cells are reprogrammed to consume large amounts of glucose to support anabolic biosynthetic pathways. However, blood perfusion and consequently the supply with glucose are frequently inadequate in solid cancers. PEPCK-M ( PCK2 ), the mitochondrial isoform of phosphoenolpyruvate carboxykinase (PEPCK), has been shown by us and others to be functionally expressed and to mediate gluconeogenesis, the reverse pathway of glycolysis, in different cancer cells. Serine and ribose synthesis have been identified as downstream pathways fed by PEPCK in cancer cells. Here, we report that PEPCK-M-dependent glycerol phosphate formation from noncarbohydrate precursors (glyceroneogenesis) occurs in starved lung cancer cells and supports de novo glycerophospholipid synthesis. Using stable isotope-labeled glutamine and lactate, we show that PEPCK-M generates phosphoenolpyruvate and 3-phosphoglycerate, which are at least partially converted to glycerol phosphate and incorporated into glycerophospholipids (GPL) under glucose and serum starvation. This pathway is required to maintain levels of GPL, especially phosphatidylethanolamine (PE), as shown by stable shRNA-mediated silencing of PEPCK-M in H23 lung cancer cells. PEPCK-M shRNA led to reduced colony formation after starvation, and the effect was partially reversed by the addition of dioleyl-PE. Furthermore, PEPCK-M silencing abrogated cancer growth in a lung cancer cell xenograft model. In conclusion, glycerol phosphate formation for de novo GPL synthesis via glyceroneogenesis is a newly characterized anabolic pathway in cancer cells mediated by PEPCK-M under conditions of severe nutrient deprivation. Copyright © 2018 the Author(s). Published by PNAS.

  13. Laser-induced particle size tuning and structural transformations in germanium nanoparticles prepared by stain etching and colloidal synthesis route

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

    Karatutlu, Ali, E-mail: a.karatutlu@qmul.ac.uk, E-mail: ali.karatutlu@bou.edu.tr; Electrical and Electronics Engineering, Bursa Orhangazi University, 16310 Yıldırım/Bursa; Little, William

    In this study, with the aid of Raman measurements, we have observed transformations in small (∼3 nm and ∼10 nm) free-standing Ge nanoparticles under laser light exposure. The nanoparticles were obtained by the chemical stain etching of a monocrystalline Ge wafer and of Ge powder and by colloidal synthesis route. We found that the transformation path depends on laser power and exposure time. At relatively low values of the laser power (2 mW) over a period of 100 min, the Raman signal indicates transformation of the sample from a nanocrystaline to bulk-like state, followed by partial oxidation and finally a conversion of themore » entire sample into alpha-quartz type GeO{sub 2}. However, when the laser power is set at 60 mW, we observed a heat release during an explosive crystallization of the nanocrystalline material into bulk Ge without noticeable signs of oxidation. Together with the transmission electron microscopy measurements, these results suggest that the chemical stain etching method for the preparation of porous Ge may not be a top-down process as has been widely considered, but a bottom up one. Systematic studies of the laser exposure on Ge nanoparticles prepared by colloidal synthesis results in the fact that the explosive crystallisation is common for H-terminated and partially disordered Ge nanoparticles regardless of its particle size. We suggest possible bio-medical applications for the observed phenomena.« less

  14. The glycerol backbone of phospholipids derives from noncarbohydrate precursors in starved lung cancer cells

    PubMed Central

    Trötzmüller, Martin; Hinteregger, Barbara; Leko, Petra; Wieser, Beatrix I.; Grasmann, Gabriele; Bertsch, Alexandra L.; Züllig, Thomas; Stacher, Elvira; Valli, Alessandro; Prassl, Ruth; Olschewski, Andrea; Harris, Adrian L.; Köfeler, Harald C.; Olschewski, Horst; Hrzenjak, Andelko

    2018-01-01

    Cancer cells are reprogrammed to consume large amounts of glucose to support anabolic biosynthetic pathways. However, blood perfusion and consequently the supply with glucose are frequently inadequate in solid cancers. PEPCK-M (PCK2), the mitochondrial isoform of phosphoenolpyruvate carboxykinase (PEPCK), has been shown by us and others to be functionally expressed and to mediate gluconeogenesis, the reverse pathway of glycolysis, in different cancer cells. Serine and ribose synthesis have been identified as downstream pathways fed by PEPCK in cancer cells. Here, we report that PEPCK-M–dependent glycerol phosphate formation from noncarbohydrate precursors (glyceroneogenesis) occurs in starved lung cancer cells and supports de novo glycerophospholipid synthesis. Using stable isotope-labeled glutamine and lactate, we show that PEPCK-M generates phosphoenolpyruvate and 3-phosphoglycerate, which are at least partially converted to glycerol phosphate and incorporated into glycerophospholipids (GPL) under glucose and serum starvation. This pathway is required to maintain levels of GPL, especially phosphatidylethanolamine (PE), as shown by stable shRNA-mediated silencing of PEPCK-M in H23 lung cancer cells. PEPCK-M shRNA led to reduced colony formation after starvation, and the effect was partially reversed by the addition of dioleyl-PE. Furthermore, PEPCK-M silencing abrogated cancer growth in a lung cancer cell xenograft model. In conclusion, glycerol phosphate formation for de novo GPL synthesis via glyceroneogenesis is a newly characterized anabolic pathway in cancer cells mediated by PEPCK-M under conditions of severe nutrient deprivation. PMID:29844165

  15. Facile bottom-up synthesis of partially oxidized black phosphorus nanosheets as metal-free photocatalyst for hydrogen evolution.

    PubMed

    Tian, Bin; Tian, Bining; Smith, Bethany; Scott, M C; Lei, Qin; Hua, Ruinian; Tian, Yue; Liu, Yi

    2018-04-24

    Few-layer black phosphorus (BP) nanosheets were first reported as a 2D material for the application of field-effect transistors in 2014 and have stimulated intense activity among physicists, chemists, and material and biomedical scientists, driving research into novel synthetic techniques to produce BP nanosheets. At present, exfoliation is the main route toward few-layer BP nanosheets via employing bulk BP as raw material. However, this is a complicated and time-consuming process, which is difficult for the large-scale synthesis of BP nanosheets. Moreover, BP degrades rapidly when exfoliated to nanoscale dimensions, resulting in the rapid loss of semiconducting properties. Here, we report the direct wet-chemical synthesis of few-layer BP nanosheets in gram-scale quantities in a bottom-up approach based on common laboratory reagents at low temperature, showing excellent stability due to partial oxidation of surface. Solvent and temperature are two critical factors, controlling not only the formation of BP nanosheets but also the thickness. The as-prepared BP nanosheets can extract hydrogen from pure water (pH = 6.8), exhibiting more than 24-fold higher activity than the well-known C 3 N 4 nanosheets. Our results reporting the ability to prepare few-layer BP nanosheets with a facile, scalable, low-cost approach take us a step closer to real-world applications of phosphorene including next-generation metal-free photocatalysts for photosynthesis. Copyright © 2018 the Author(s). Published by PNAS.

  16. A Consumer's Guide to Benchmark Dose Models: Results of U.S. EPA Testing of 14 Dichotomous, 8 Continuous, and 6 Developmental Models (Presentation)

    EPA Science Inventory

    Benchmark dose risk assessment software (BMDS) was designed by EPA to generate dose-response curves and facilitate the analysis, interpretation and synthesis of toxicological data. Partial results of QA/QC testing of the EPA benchmark dose software (BMDS) are presented. BMDS pr...

  17. Preliminary study on chicken feather protein-based wood adhesives

    Treesearch

    Zehui Jiang; Daochun Qin; Chung-Yun Hse; Monlin Kuo; Zhaohui Luo; Ge Wang; Yan Yu

    2008-01-01

    The objective of this preliminary study was to partially replace phenol in the synthesis of phenol-formaldehyde resin with feather protein. Feather protein–based resins, which contained one part feather protein and two parts phenol, were formulated under the conditions of two feather protein hydrolysis methods (with and without presence of phenol during...

  18. Transamination at the Crossroad of the One-Pot Synthesis of N-Substituted Quinonediimines and C-Substituted Benzobisimidazoles.

    PubMed

    Andeme Edzang, Judicaelle; Chen, Zhongrui; Audi, Hassib; Canard, Gabriel; Siri, Olivier

    2016-10-10

    A green and very efficient synthesis of N-substituted benzoquinonediimines or C-substituted benzo-bis(imidazole) derivatives is described under similar conditions. The different reaction pathway is only controlled by the nature of the primary amines, which tunes the reactivity of the intermediates.

  19. Efficient synthesis of methylene exo-glycals: another use of glycosylthiomethyl chlorides.

    PubMed

    Zhu, Xiangming; Jin, Ying; Wickham, John

    2007-03-30

    A new approach to the synthesis of methylene exo-glycals is described. Oxidation of glycosylthiolmethyl chloride (GTM-Cl) with mCPBA afforded the corresponding glycosylchloromethyl sulfone in almost quantitative yield, which underwent KOtBu-induced Ramberg-Bäcklund rearrangement to furnish the desired methylene exo-glycal in excellent yield.

  20. Pd-catalyzed one-pot synthesis of polysubstituted acrylamidines from isocyanides, diazo compounds, and imines.

    PubMed

    Yan, Xu; Liao, Jinxi; Lu, Yongzhi; Liu, Jinsong; Zeng, Youlin; Cai, Qian

    2013-05-17

    A novel and efficient Pd-catalyzed one-pot reaction of ethyl diazoacetate, isocyanides, and imines for the synthesis of acrylamidines was developed. The multicomponent reaction may have occurred through an unpredicted ring-opening process of the ketenimine-imine [2 + 2] intermediate to form the acrylamidine products.

  1. Rhodium-catalyzed synthesis of silafluorene derivatives via cleavage of silicon-hydrogen and carbon-hydrogen bonds.

    PubMed

    Ureshino, Tomonari; Yoshida, Takuya; Kuninobu, Yoichiro; Takai, Kazuhiko

    2010-10-20

    The rhodium-catalyzed synthesis of silafluorenes from biphenylhydrosilanes is described. This highly efficient reaction proceeds via both Si-H and C-H bond activation, producing only H(2) as a side product. Using this method, a ladder-type bis-silicon-bridged p-terphenyl could also be synthesized.

  2. Synthesis and antibacterial activity of novel enolphosphate derivatives.

    PubMed

    Grison, Claude; Barthes, Nicolas; Finance, Chantal; Duval, Raphael E

    2010-10-01

    A new class of enolphosphates derivatives, the 1-alkenyldiphosphates, was designed and a rapid and efficient synthesis for these compounds was developed. These new molecules showed interesting in vitro antibacterial activities (MIC) against Gram-positive bacteria (Staphylococcus aureus) and Gram-negative pathogens including Pseudomonas aeruginosa and Escherichia coli. 2010 Elsevier Inc. All rights reserved.

  3. Microwave assisted synthesis of bridgehead alkenes.

    PubMed

    Cleary, Leah; Yoo, Hoseong; Shea, Kenneth J

    2011-04-01

    A new, concise method to synthesize triene precursors for the type 2 intramolecular Diels-Alder reaction has been developed. Microwave irradiation of the trienes provides a convenient method for the synthesis of bridgehead alkenes. Higher yields, shorter reaction times, and lower reaction temperatures provide a general and efficient route to this interesting class of molecules.

  4. Microwave Assisted Synthesis of Bridgehead Alkenes

    PubMed Central

    Cleary, Leah; Yoo, Hoseong; Shea, Kenneth J.

    2011-01-01

    A new, concise method to synthesize triene precursors for the type 2 intramolecular Diels–Alder reaction has been developed. Microwave irradiation of the trienes provides a convenient method for the synthesis of bridgehead alkenes. Higher yields, shorter reaction times and lower reaction temperatures provide a general and efficient route to this interesting class of molecules. PMID:21384818

  5. A new practical approach towards the synthesis of unsymmetric and symmetric 1,10-phenanthroline derivatives at room temperature.

    PubMed

    Cheng, Yongfeng; Han, Xuesong; Ouyang, Huangche; Rao, Yu

    2012-03-18

    An efficient method towards synthesis of 1,10-phenanthrolines is described. Through Lewis acid-catalyzed annulation reaction between 3-ethoxycyclobutanones and 8-aminoquinolines, a variety of unsymmetric and symmetric 1,10-phenanthroline derivatives were readily prepared with high regioselectivity at room temperature.

  6. Apparatus for the laser ablative synthesis of carbon nanotubes

    DOEpatents

    Smith, Michael W.; Jordan, Kevin

    2010-02-16

    An RF-induction heated side-pumped synthesis chamber for the production of carbon nanotubes. Such an apparatus, while capable of producing large volumes of carbon nanotubes, concurrently provides a simplified apparatus that allows for greatly reduced heat up and cool down times and flexible flowpaths that can be readily modified for production efficiency optimization.

  7. Low‐Temperature Combustion Synthesis of a Spinel NiCo2O4 Hole Transport Layer for Perovskite Photovoltaics

    PubMed Central

    Papadas, Ioannis T.; Ioakeimidis, Apostolos; Armatas, Gerasimos S.

    2018-01-01

    Abstract The synthesis and characterization of low‐temperature solution‐processable monodispersed nickel cobaltite (NiCo2O4) nanoparticles (NPs) via a combustion synthesis is reported using tartaric acid as fuel and the performance as a hole transport layer (HTL) for perovskite solar cells (PVSCs) is demonstrated. NiCo2O4 is a p‐type semiconductor consisting of environmentally friendly, abundant elements and higher conductivity compared to NiO. It is shown that the combustion synthesis of spinel NiCo2O4 using tartaric acid as fuel can be used to control the NPs size and provide smooth, compact, and homogeneous functional HTLs processed by blade coating. Study of PVSCs with different NiCo2O4 thickness as HTL reveals a difference on hole extraction efficiency, and for 15 nm, optimized thickness enhanced hole carrier collection is achieved. As a result, p‐i‐n structure of PVSCs with 15 nm NiCo2O4 HTLs shows reliable performance and power conversion efficiency values in the range of 15.5% with negligible hysteresis. PMID:29876223

  8. Nonenzymatic template-directed synthesis on hairpin oligonucleotides. 3. Incorporation of adenosine and uridine residues

    NASA Technical Reports Server (NTRS)

    Wu, T.; Orgel, L. E.

    1992-01-01

    We have used [32P]-labeled hairpin oligonucleotides to study template-directed synthesis on templates containing one or more A or T residues within a run of C residues. When nucleoside-5'-phosphoro(2-methyl)imidazolides are used as substrates, isolated A and T residues function efficiently in facilitating the incorporation of U and A, respectively. The reactions are regiospecific, producing mainly 3'-5'-phosphodiester bonds. Pairs of consecutive non-C residues are copied much less efficiently. Limited synthesis of CA and AC sequences on templates containing TG and GT sequences was observed along with some synthesis of the AA sequences on templates containing TT sequences. The other dimer sequences investigated, AA, AG, GA, TA, and AT, could not be copied. If A is absent from the reaction mixture, misincorporation of G residues is a significant reaction on templates containing an isolated T residue or two consecutive T residues. However, if both A and G are present, A is incorporated to a much greater extent than G. We believe that wobble-pairing between T and G is responsible for misincorporation when only G is present.

  9. Plasma-Assisted Synthesis and Surface Modification of Electrode Materials for Renewable Energy.

    PubMed

    Dou, Shuo; Tao, Li; Wang, Ruilun; El Hankari, Samir; Chen, Ru; Wang, Shuangyin

    2018-05-01

    Renewable energy technology has been considered as a "MUST" option to lower the use of fossil fuels for industry and daily life. Designing critical and sophisticated materials is of great importance in order to realize high-performance energy technology. Typically, efficient synthesis and soft surface modification of nanomaterials are important for energy technology. Therefore, there are increasing demands on the rational design of efficient electrocatalysts or electrode materials, which are the key for scalable and practical electrochemical energy devices. Nevertheless, the development of versatile and cheap strategies is one of the main challenges to achieve the aforementioned goals. Accordingly, plasma technology has recently appeared as an extremely promising alternative for the synthesis and surface modification of nanomaterials for electrochemical devices. Here, the recent progress on the development of nonthermal plasma technology is highlighted for the synthesis and surface modification of advanced electrode materials for renewable energy technology including electrocatalysts for fuel cells, water splitting, metal-air batteries, and electrode materials for batteries and supercapacitors, etc. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Synthesis and Luminescence Characteristics of Cr 3+ doped Y 3Al 5O 12 Phosphors

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

    Smith, Brenda A.; Dabestani, Reza T.; Lewis, Linda A.

    2015-10-01

    Luminescence performance of yttrium aluminum garnet (Y 3Al 5O 12) phosphors as a function of Cr 3+ concentration has been investigated via two different wet-chemical synthesis techniques, direct- (DP) and hydrothermal-precipitation (HP). Using either of these methods, the red-emitting phosphor [Y 3Al 5-xCr xO 12 (YAG: Cr 3+)] showed similar photoluminescence (PL) intensities once the dopant concentration was optimized. Specifically, the YAG: Cr 3+ PL emission intensity reached a maximum at Cr3+ concentrations of x = 0.02 (0.4 at.%) and x = 0.13 (2.6 at.%) for DP and HP processed samples, respectively. The results indicated the strong influence of themore » processing method on the optimized YAG: Cr 3+ performance, where a more effective energy transfer rate between a pair of Cr3+ activators at low concentration levels was observed by using the DP synthesis technique. Development of a highly efficient phosphor, using a facile synthesis approach, could significantly benefit consumer and industrial applications by improving the operational efficiency of a wide range of practical devices.« less

  11. Synthesis of energy-efficient FSMs implemented in PLD circuits

    NASA Astrophysics Data System (ADS)

    Nawrot, Radosław; Kulisz, Józef; Kania, Dariusz

    2017-11-01

    The paper presents an outline of a simple synthesis method of energy-efficient FSMs. The idea consists in using local clock gating to selectively block the clock signal, if no transition of a state of a memory element is required. The research was dedicated to logic circuits using Programmable Logic Devices as the implementation platform, but the conclusions can be applied to any synchronous circuit. The experimental section reports a comparison of three methods of implementing sequential circuits in PLDs with respect to clock distribution: the classical fully synchronous structure, the structure exploiting the Enable Clock inputs of memory elements, and the structure using clock gating. The results show that the approach based on clock gating is the most efficient one, and it leads to significant reduction of dynamic power consumed by the FSM.

  12. EGF receptor tyrosine kinase inhibitors diminish transforming growth factor-alpha-induced pulmonary fibrosis.

    PubMed

    Hardie, William D; Davidson, Cynthia; Ikegami, Machiko; Leikauf, George D; Le Cras, Timothy D; Prestridge, Adrienne; Whitsett, Jeffrey A; Korfhagen, Thomas R

    2008-06-01

    Transforming growth factor-alpha (TGF-alpha) is a ligand for the EGF receptor (EGFR). EGFR activation is associated with fibroproliferative processes in human lung disease and animal models of pulmonary fibrosis. We determined the effects of EGFR tyrosine kinase inhibitors gefitinib (Iressa) and erlotinib (Tarceva) on the development and progression of TGF-alpha-induced pulmonary fibrosis. Using a doxycycline-regulatable transgenic mouse model of lung-specific TGF-alpha expression, we determined effects of treatment with gefitinib and erlotinib on changes in lung histology, total lung collagen, pulmonary mechanics, pulmonary hypertension, and expression of genes associated with synthesis of ECM and vascular remodeling. Induction in the lung of TGF-alpha caused progressive pulmonary fibrosis over an 8-wk period. Daily administration of gefitinib or erlotinib prevented development of fibrosis, reduced accumulation of total lung collagen, prevented weight loss, and prevented changes in pulmonary mechanics. Treatment of mice with gefitinib 4 wk after the induction of TGF-alpha prevented further increases in and partially reversed total collagen levels and changes in pulmonary mechanics and pulmonary hypertension. Increases in expression of genes associated with synthesis of ECM as well as decreases of genes associated with vascular remodeling were also prevented or partially reversed. Administration of gefitinib or erlotinib did not cause interstitial fibrosis or increases in lavage cell counts. Administration of small molecule EGFR tyrosine kinase inhibitors prevented further increases in and partially reversed pulmonary fibrosis induced directly by EGFR activation without inducing inflammatory cell influx or additional lung injury.

  13. Synthesis and screening of one-bead-one-compound cyclic peptide libraries.

    PubMed

    Qian, Ziqing; Upadhyaya, Punit; Pei, Dehua

    2015-01-01

    Cyclic peptides have been a rich source of biologically active molecules. Herein we present a method for the combinatorial synthesis and screening of large one-bead-one-compound (OBOC) libraries of cyclic peptides against biological targets such as proteins. Up to ten million different cyclic peptides are rapidly synthesized on TentaGel microbeads by the split-and-pool synthesis method and subjected to a multistage screening protocol which includes magnetic sorting, on-bead enzyme-linked and fluorescence-based assays, and in-solution binding analysis of cyclic peptides selectively released from single beads by fluorescence anisotropy. Finally, the most active hit(s) is identified by the partial Edman degradation-mass spectrometry (PED-MS) method. This method allows a single researcher to synthesize and screen up to ten million cyclic peptides and identify the most active ligand(s) in ~1 month, without the time-consuming and expensive hit resynthesis or the use of any special equipment.

  14. Control of Chondrogenesis in Limb-Bud Cell Cultures by Bromodeoxyuridine

    PubMed Central

    Levitt, Daniel; Doreman, Albert

    1973-01-01

    Initial exposure of cultured limb-bud cells (stage 23-24) to 5-bromo-2′-deoxyuridine (BrdU) irreversibly inhibits differentiation to cartilage under three different culture conditions. The inhibition of chondroitin sulfate synthesis is partially reversed by D-xylose in limb-bud cells after treatment with BrdU. The activities of four enzymes involved in chondroitin sulfate production were reduced in BrdU-treated cultures, but the magnitude of decrease was far less than the decrease in glycosaminoglycan synthesis. The slight increase in the turnover rate of sulfated glycosaminoglycans in BrdU-treated mesenchyme was not sufficient to account for the marked decrease in chondroitin sulfate content. The results suggest that BrdU treatment interferes with normal synthesis of chondroitin sulfate core protein in cultured limb-bud cells, but does not greatly diminish enzyme activities or UDP-sugar levels necessary for production of polysaccharide chains. PMID:4275762

  15. CMG–Pol epsilon dynamics suggests a mechanism for the establishment of leading-strand synthesis in the eukaryotic replisome

    PubMed Central

    Janska, Agnieszka; Goswami, Panchali; Renault, Ludovic; Abid Ali, Ferdos; Kotecha, Abhay; Costa, Alessandro

    2017-01-01

    The replisome unwinds and synthesizes DNA for genome duplication. In eukaryotes, the Cdc45–MCM–GINS (CMG) helicase and the leading-strand polymerase, Pol epsilon, form a stable assembly. The mechanism for coupling DNA unwinding with synthesis is starting to be elucidated, however the architecture and dynamics of the replication fork remain only partially understood, preventing a molecular understanding of chromosome replication. To address this issue, we conducted a systematic single-particle EM study on multiple permutations of the reconstituted CMG–Pol epsilon assembly. Pol epsilon contains two flexibly tethered lobes. The noncatalytic lobe is anchored to the motor of the helicase, whereas the polymerization domain extends toward the side of the helicase. We observe two alternate configurations of the DNA synthesis domain in the CMG-bound Pol epsilon. We propose that this conformational switch might control DNA template engagement and release, modulating replisome progression. PMID:28373564

  16. Translational Control of Hemoglobin Synthesis by an Initiation Factor Required for Recycling of Ribosomes and for their Binding to Messenger RNA

    PubMed Central

    Kaempfer, Raymond; Kaufman, Jennifer

    1972-01-01

    The continued recycling of ribosomes during protein synthesis in rabbit reticulocyte lysates at 37° requires an initiation factor whose activity is rapidly lost in the absence of added heme. Partially purified factor (i) fully maintains the polysomes; (ii) inhibits the association of 40S and 60S ribosomal subunits into single ribosomes; (iii) promotes the quantitative entry of added 60S subunits into polysomes; (iv) allows the accumulation of ribosomal subunits, instead of single ribosomes, when initiation is blocked with aurin tricarboxylate; and (v) is absolutely required for the binding of globin messenger RNA to ribosomes. These properties suggest that this mammalian initiation factor functions analogously to bacterial IF-3. In addition, the translational control of globin synthesis by heme is exerted, directly or indirectly, through this factor. PMID:4508325

  17. Highly efficient solid phase synthesis of oligonucleotide analogs containing phosphorodithioate linkages.

    PubMed

    Capaldi, D C; Cole, D L; Ravikumar, V T

    2000-05-01

    A triester method for the synthesis of deoxynucleoside phosphorodithioate dimers is described. The phosphorodithioate linkage is introduced using a new dithiophosphorylating reagent DPSE-SP(S)Cl(2)where DPSE = 2-diphenylmethylsilylethyl. This group is removed quickly using tetra-butylammonium fluoride leading to the quantitative formation of phosphorodithioate diesters uncontaminated with the corresponding phosphorothioates. The utility of this group is demonstrated by the synthesis of a penta-decathymidylic acid, [T(PS(2))T(PO(2))](7)T, which contains alternating phosphorodithioate/phosphate diester internucleotide linkages.

  18. Synthesis of S-linked trisaccharide glycal of derhodinosylurdamycin A: Discovery of alkyl thiocyanate as an efficient electrophile for stereoselective sulfenylation of 2-deoxy glycosyl lithium.

    PubMed

    Acharya, Padam P; Baryal, Kedar N; Reno, Cristin E; Zhu, Jianglong

    2017-08-07

    Stereoselective synthesis of S-linked trisaccharide glycal of angucycline antitumor antibiotic derhodinosylurdamycin A is described. The synthesis has been accomplished employing our previously reported umpolung S-glycosylation strategy - stereoselective sulfenylation of 2-deoxy glycosyl lithium. It was found that sugar-derived thiocyanate was a better electrophile than corresponding asymmetric disulfide in this type of stereoselective sulfenylation. Copyright © 2017 Elsevier Ltd. All rights reserved.

  19. Parallel synthesis of ureas and carbamates from amines and CO2 under mild conditions.

    PubMed

    Peterson, Scott L; Stucka, Sabrina M; Dinsmore, Christopher J

    2010-03-19

    A mild and efficient library synthesis technique has been developed for the synthesis of ureas and carbamates from carbamic acids derived from the DBU-catalyzed reaction of amines and gaseous carbon dioxide. Carbamic acids derived from primary amines reacted with Mitsunobu reagents to generate isocyanates in situ which were condensed with primary and secondary amines to afford the desired ureas. Similarly, carbamic acids from secondary amines reacted with alcohols activated with Mitsunobu reagents to form carbamates.

  20. Discovery and gram-scale synthesis of BMS-593214, a potent, selective FVIIa inhibitor

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

    Priestley, E. Scott; De Lucca, Indawati; Zhou, Jinglan

    A 6-amidinotetrahydroquinoline screening hit was driven to a structurally novel, potent, and selective FVIIa inhibitor through a combination of library synthesis and rational design. An efficient gram-scale synthesis of the active enantiomer BMS-593214 was developed, which required significant optimization of the key Povarov annulation. Importantly, BMS-593214 showed antithrombotic efficacy in a rabbit arterial thrombosis model. A crystal structure of BMS-593214 bound to FVIIa highlights key contacts with Asp 189, Lys 192, and the S2 pocket.

  1. Proceedings of the International Conference on Lasers 󈨛 Held at Lake Tahoe, Nevada on 7-11 December 1987.

    DTIC Science & Technology

    1988-01-01

    the synthesis . DONOR • - TRIPLETLAE DY QUUENCHER Figure 1 Scheme of an ideal laser dyel. More realistic improvements in the development of new and...fluorescence efficiency and bathochromic spectral shifts are the 7-julolidylcoumarins as shown in the general structure 1 . R, The synthesis of these...julolidylcoumarins is depicted in Scheme 1 . The most critical step in the entire synthesis is the preparation of 8-hydroxyjulolidine which was formed in

  2. Total Synthesis of the Post-translationally Modified Polyazole Peptide Antibiotic Goadsporin.

    PubMed

    Dexter, Hannah L; Williams, Huw E L; Lewis, William; Moody, Christopher J

    2017-03-06

    The structurally unique polyazole antibiotic goadsporin contains six heteroaromatic oxazole and thiazole rings integrated into a linear array of amino acids that also contains two dehydroalanine residues. An efficient total synthesis of goadsporin is reported in which the key steps are the use of rhodium(II)-catalyzed reactions of diazocarbonyl compounds to generate the four oxazole rings, which demonstrates the power of rhodium carbene chemistry in organic chemical synthesis. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Stereoselective protecting group free synthesis of D,L-gulose ethyl glycoside via multicomponent enyne cross metathesis--hetero Diels-Alder reaction.

    PubMed

    Castagnolo, Daniele; Botta, Lorenzo; Botta, Maurizio

    2009-07-27

    An efficient and stereoselective synthesis of D,L-gulose was described. The key step of the synthetic route is represented by a multicomponent enyne cross metathesis-hetero Diels-Alder reaction which allows the formation of the pyran ring from cheap and commercially available substrates in a single synthetic step. The synthesis of D,L-gulose was accomplished without the use of protecting groups making this approach highly desirable also in terms of atom economy.

  4. Regio- and enantioselective synthesis of N-substituted pyrazoles by rhodium-catalyzed asymmetric addition to allenes.

    PubMed

    Haydl, Alexander M; Xu, Kun; Breit, Bernhard

    2015-06-08

    The rhodium-catalyzed asymmetric N-selective coupling of pyrazole derivatives with terminal allenes gives access to enantioenriched secondary and tertiary allylic pyrazoles, which can be employed for the synthesis of medicinally important targets. The reaction tolerates a large variety of functional groups and labelling experiments gave insights into the reaction mechanism. This new methodology was further applied in a highly efficient synthesis of JAK 1/2 inhibitor (R)-ruxolitinib. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Stereoselectivity in N-Iminium Ion Cyclization: Development of an Efficient Synthesis of (±)-Cephalotaxine.

    PubMed

    Liu, Hao; Yu, Jing; Li, Xinyu; Yan, Rui; Xiao, Ji-Chang; Hong, Ran

    2015-09-18

    A stereoselective N-iminium ion cyclization with allylsilane to construct vicinal quaternary-tertiary carbon centers was developed for the concise synthesis of (±)-cephalotaxine. The current strategy features a TiCl4-promoted cyclization and ring-closure metathesis to furnish the spiro-ring system. The stereochemical outcome in the N-acyliminium ion cyclization was rationalized by the stereoelectronic effect of the Z- or E-allylsilane. Two diastereomers arising from the cyclization were merged into the formal synthesis of (±)-cephalotaxine.

  6. Efficiency and Fidelity of Human DNA Polymerases λ and β during Gap-Filling DNA Synthesis

    PubMed Central

    Brown, Jessica A.; Pack, Lindsey R.; Sanman, Laura E.; Suo, Zucai

    2010-01-01

    The base excision repair (BER) pathway coordinates the replacement of 1 to 10 nucleotides at sites of single-base lesions. This process generates DNA substrates with various gap sizes which can alter the catalytic efficiency and fidelity of a DNA polymerase during gap-filling DNA synthesis. Here, we quantitatively determined the substrate specificity and base substitution fidelity of human DNA polymerase λ (Pol λ), an enzyme proposed to support the known BER DNA polymerase β (Pol β), as it filled 1- to 10-nucleotide gaps at 1-nucleotide intervals. Pol λ incorporated a correct nucleotide with relatively high efficiency until the gap size exceeded 9 nucleotides. Unlike Pol λ, Pol β did not have an absolute threshold on gap size as the catalytic efficiency for a correct dNTP gradually decreased as the gap size increased from 2 to 10 nucleotides and then recovered for non-gapped DNA. Surprisingly, an increase in gap size resulted in lower polymerase fidelity for Pol λ, and this downregulation of fidelity was controlled by its non-enzymatic N-terminal domains. Overall, Pol λ was up to 160-fold more error-prone than Pol β, thereby suggesting Pol λ would be more mutagenic during long gap-filling DNA synthesis. In addition, dCTP was the preferred misincorporation for Pol λ and its N-terminal domain truncation mutants. This nucleotide preference was shown to be dependent upon the identity of the adjacent 5′-template base. Our results suggested that both Pol λ and Pol β would catalyze nucleotide incorporation with the highest combination of efficiency and accuracy when the DNA substrate contains a single-nucleotide gap. Thus, Pol λ, like Pol β, is better suited to catalyze gap-filling DNA synthesis during short-patch BER in vivo, although, Pol λ may play a role in long-patch BER. PMID:20961817

  7. Amino acid substrates impose polyamine, eIF5A, or hypusine requirement for peptide synthesis.

    PubMed

    Shin, Byung-Sik; Katoh, Takayuki; Gutierrez, Erik; Kim, Joo-Ran; Suga, Hiroaki; Dever, Thomas E

    2017-08-21

    Whereas ribosomes efficiently catalyze peptide bond synthesis by most amino acids, the imino acid proline is a poor substrate for protein synthesis. Previous studies have shown that the translation factor eIF5A and its bacterial ortholog EF-P bind in the E site of the ribosome where they contact the peptidyl-tRNA in the P site and play a critical role in promoting the synthesis of polyproline peptides. Using misacylated Pro-tRNAPhe and Phe-tRNAPro, we show that the imino acid proline and not tRNAPro imposes the primary eIF5A requirement for polyproline synthesis. Though most proline analogs require eIF5A for efficient peptide synthesis, azetidine-2-caboxylic acid, a more flexible four-membered ring derivative of proline, shows relaxed eIF5A dependency, indicating that the structural rigidity of proline might contribute to the requirement for eIF5A. Finally, we examine the interplay between eIF5A and polyamines in promoting translation elongation. We show that eIF5A can obviate the polyamine requirement for general translation elongation, and that this activity is independent of the conserved hypusine modification on eIF5A. Thus, we propose that the body of eIF5A functionally substitutes for polyamines to promote general protein synthesis and that the hypusine modification on eIF5A is critically important for poor substrates like proline. Published by Oxford University Press on behalf of Nucleic Acids Research 2017.

  8. Adult Polyglucosan Body Disease (APBD): Anaplerotic diet therapy (Triheptanoin) and demonstration of defective methylation pathways.

    PubMed

    Roe, Charles R; Bottiglieri, Teodoro; Wallace, Mary; Arning, Erland; Martin, Alan

    2010-01-01

    APBD is a rare disorder most often affecting adults of Ashkenazi Jewish origin due to partial deficiency of the glycogen brancher enzyme (GBE). It is characterized by progressive involvement of both the central and peripheral nervous systems and deposition of amylopectin-like polyglucosan bodies. There have been no metabolic derangements that might suggest effective therapy nor have there been any clinical improvements for control of its relentless progression. The APBD patients, in this study, experienced stabilization of disease progression, and limited functional improvement in most patients with dietary triheptanoin. Due to a plateau in clinical improvement, the reduced plasma creatinine and methionine levels prompted evaluation of other plasma methylation intermediates in this complex integrated pathway system: decreased S-adenosylmethionine (SAM) (p<0.002), increased S-adenosylhomocysteine (p<0.001), elevated creatine (p=0.001) and increased free choline (p<0.001). Plasma levels of homocysteine and guanidinoacetate were normal. Impaired metabolism of choline and creatine may relate to the progressive dysmyelination and progressive muscle weakness associated with APBD. The partial deficiency of GBE appears to produce a secondary energy deficit possibly related to inadequate reserves of normal glycogen for efficient degradation to free glucose. Dysfunctional regulation of glycogen synthase (GS) may result in continued synthesis and deposition of polyglucosan bodies. This investigation has demonstrated, for the first time, arrest of clinical deterioration with limited functional recovery with triheptanoin diet therapy and the existence of significant derangement of methylation pathways that, when corrected, may lead to even greater therapeutic benefits. Copyright © 2010 Elsevier Inc. All rights reserved.

  9. [11C]choline uptake in regenerating liver after partial hepatectomy or CCl4-administration.

    PubMed

    Sasaki, Toru

    2004-02-01

    To characterize [methyl-(11)C]choline ([(11)C]choline) as an oncologic PET radiopharmaceutical, [(11)C]choline uptake in regenerating livers after partial hepatectomy as a model of typical proliferating tissue and after CCl(4) insult as that of proliferating tissue with inflammation, was studied in rats. [(11)C]Choline, [(18)F]2-fluoro-2-deoxy-D-glucose ([(18)F]FDG) and [2-(14)C]thymidine ([(14)C]TdR) uptake was studied in regenerating rat liver after 70% partial hepatectomy or CCl(4)-administration. [(11)C]Choline uptake in regenerating liver after partial hepatectomy was significantly increased with [(14)C]TdR uptake as a marker of DNA synthesis at 18 hours after surgery. On the other hand, the uptake was not accelerated by CCl(4)-administration, though it significantly increased [(14)C]TdR uptake. There were no differences of [(11)C]choline uptake acceleration following partial hepatectomy among the three parts of the regenerating liver. [(18)F]FDG uptake was accelerated in the regenerating liver on either partial hepatectomy or CCl(4)-administration. The magnitude of the increase in [(18)F]FDG uptake in the regenerating liver induced by partial hepatectomy was greater than that for [(11)C]choline. [(11)C]Choline uptake in the liver was accelerated by partial hepatectomy, but not by CCl(4)-administration. This might be expected given that the differentiation between proliferating tissues such as tumor and inflammatory tissue was possible by [(11)C]choline-PET.

  10. Improvement of dry fractionation ethanol fermentation by partial germ supplementation

    USDA-ARS?s Scientific Manuscript database

    Ethanol fermentation of dry fractionated grits (corn endosperm pieces) containing different levels of germ was studied using the dry grind process. Partial removal of germ fraction allows for marketing the germ fraction and potentially more efficient fermentation. Grits obtained from a dry milling p...

  11. Tailor Made Synthesis of T-Shaped and π-STACKED Dimers in the Gas Phase: Concept for Efficient Drug Design and Material Synthesis

    NASA Astrophysics Data System (ADS)

    Kumar, Sumit; Das, Aloke

    2013-06-01

    Non-covalent interactions play a key role in governing the specific functional structures of biomolecules as well as materials. Thus molecular level understanding of these intermolecular interactions can help in efficient drug design and material synthesis. It has been found from X-ray crystallography that pure hydrocarbon solids (i.e. benzene, hexaflurobenzene) have mostly slanted T-shaped (herringbone) packing arrangement whereas mixed solid hydrocarbon crystals (i.e. solid formed from mixtures of benzene and hexafluorobenzene) exhibit preferentially parallel displaced (PD) π-stacked arrangement. Gas phase spectroscopy of the dimeric complexes of the building blocks of solid pure benzene and mixed benzene-hexafluorobenzene adducts exhibit similar structural motifs observed in the corresponding crystal strcutures. In this talk, I will discuss about the jet-cooled dimeric complexes of indole with hexafluorobenzene and p-xylene in the gas phase using Resonant two photon ionzation and IR-UV double resonance spectroscopy combined with quantum chemistry calculations. In stead of studying benzene...p-xylene and benzene...hexafluorobenzene dimers, we have studied corresponding indole complexes because N-H group is much more sensitive IR probe compared to C-H group. We have observed that indole...hexafluorobenzene dimer has parallel displaced (PD) π-stacked structure whereas indole...p-xylene has slanted T-shaped structure. We have shown here selective switching of dimeric structure from T-shaped to π-stacked by changing the substituent from electron donating (-CH3) to electron withdrawing group (fluorine) in one of the complexing partners. Thus, our results demonstrate that efficient engineering of the non-covalent interactions can lead to efficient drug design and material synthesis.

  12. Template Dimerization Promotes an Acceptor Invasion-Induced Transfer Mechanism during Human Immunodeficiency Virus Type 1 Minus-Strand Synthesis

    PubMed Central

    Balakrishnan, Mini; Roques, Bernard P.; Fay, Philip J.; Bambara, Robert A.

    2003-01-01

    The biochemical mechanism of template switching by human immunodeficiency virus type 1 (HIV-1) reverse transcriptase and the role of template dimerization were examined. Homologous donor-acceptor template pairs derived from the HIV-1 untranslated leader region and containing the wild-type and mutant dimerization initiation sequences (DIS) were used to examine the efficiency and distribution of transfers. Inhibiting donor-acceptor interaction was sufficient to reduce transfers in DIS-containing template pairs, indicating that template dimerization, and not the mere presence of the DIS, promotes efficient transfers. Additionally, we show evidence that the overall transfer process spans an extended region of the template and proceeds through a two-step mechanism. Transfer is initiated through an RNase H-facilitated acceptor invasion step, while synthesis continues on the donor template. The invasion then propagates towards the primer terminus by branch migration. Transfer is completed with the translocation of the primer terminus at a site distant from the invasion point. In our system, most invasions initiated before synthesis reached the DIS. However, transfer of the primer terminus predominantly occurred after synthesis through the DIS. The two steps were separated by 60 to 80 nucleotides. Sequence markers revealed the position of primer terminus switch, whereas DNA oligomers designed to block acceptor-cDNA interactions defined sites of invasion. Within the region of homology, certain positions on the template were inherently more favorable for invasion than others. In templates with DIS, the proximity of the acceptor facilitates invasion, thereby enhancing transfer efficiency. Nucleocapsid protein enhanced the overall efficiency of transfers but did not alter the mechanism. PMID:12663778

  13. ZnO nanoparticles as an efficient, heterogeneous, reusable, and ecofriendly catalyst for four-component one-pot green synthesis of pyranopyrazole derivatives in water.

    PubMed

    Sachdeva, Harshita; Saroj, Rekha

    2013-01-01

    An extremely efficient catalytic protocol for the synthesis of a series of pyranopyrazole derivatives developed in a one-pot four-component approach in the presence of ZnO nanoparticles as heterogeneous catalyst using water as a green solvent is reported. Greenness of the process is well instituted as water is exploited both as reaction media and medium for synthesis of catalyst. The ZnO nanoparticles exhibited excellent catalytic activity, and the proposed methodology is capable of providing the desired products in good yield (85-90%) and short reaction time. After reaction course, ZnO nanoparticles can be recycled and reused without any apparent loss of activity which makes this process cost effective and hence ecofriendly. All the synthesized compounds have been characterized on the basis of elemental analysis, IR, ¹H NMR, and ¹³C NMR spectral studies.

  14. An efficient synthesis of the constrained peptidomimetic 2-oxo-3-(N-9-fluorenyloxycarbonylamino)-1-azabicyclo[4.3.0]nonane-9-carboxylic acid from pyroglutamic acid.

    PubMed

    Mandal, Pijus Kumar; Kaluarachchi, Kumar K; Ogrin, Douglas; Bott, Simon G; McMurray, John S

    2005-11-25

    [reaction: see text] Azabicyclo[X.Y.0]alkane amino acids are rigid dipeptide mimetics that are useful tools for structure-activity studies in peptide-based drug discovery. Herein, we report an efficient synthesis of three diastereomers of 9-tert-butoxycarbonyl-2-oxo-3-(N-tert-butoxycarbonylamino)-1-azabicyclo[4.3.0]nonane (3S,6S,9S, 3S,6R,9R, and 3S,6R,9S). Methyl N-Boc-pyroglutamate is cleaved with vinylmagnesium bromide to produce an acyclic gamma-vinyl ketone. Michael addition of N-diphenylmethyleneglycine tert-butyl ester produces the N-Boc-delta-oxo-alpha,omega-diaminoazelate intermediate, which, on hydrogenloysis, gives the fused ring system. Acidolytic deprotection followed by Fmoc-protection provided building blocks suitable for solid-phase synthesis.

  15. Seamless integration of dose-response screening and flow chemistry: efficient generation of structure-activity relationship data of β-secretase (BACE1) inhibitors.

    PubMed

    Werner, Michael; Kuratli, Christoph; Martin, Rainer E; Hochstrasser, Remo; Wechsler, David; Enderle, Thilo; Alanine, Alexander I; Vogel, Horst

    2014-02-03

    Drug discovery is a multifaceted endeavor encompassing as its core element the generation of structure-activity relationship (SAR) data by repeated chemical synthesis and biological testing of tailored molecules. Herein, we report on the development of a flow-based biochemical assay and its seamless integration into a fully automated system comprising flow chemical synthesis, purification and in-line quantification of compound concentration. This novel synthesis-screening platform enables to obtain SAR data on b-secretase (BACE1) inhibitors at an unprecedented cycle time of only 1 h instead of several days. Full integration and automation of industrial processes have always led to productivity gains and cost reductions, and this work demonstrates how applying these concepts to SAR generation may lead to a more efficient drug discovery process. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Aggregation and lack of secretion of most newly synthesized proinsulin in non-beta-cell lines.

    PubMed

    Zhu, Yong Lian; Abdo, Alexander; Gesmonde, Joan F; Zawalich, Kathleen C; Zawalich, Walter; Dannies, Priscilla S

    2004-08-01

    Myoblasts transfected with HB10D insulin secrete more hormone than those transfected with wild-type insulin, as published previously, indicating that production of wild-type insulin is not efficient in these cells. The ability of non-beta-cells to produce insulin was examined in several cell lines. In clones of neuroendocrine GH(4)C(1) cells stably transfected with proinsulin, two thirds of (35)S-proinsulin was degraded within 3 h of synthesis, whereas (35)S-prolactin was stable. In transiently transfected neuroendocrine AtT20 cells, half of (35)S-proinsulin was degraded within 3 h after synthesis, whereas (35)S-GH was stable. In transiently transfected fibroblast COS cells, (35)S-proinsulin was stable for longer, but less than 10% was secreted 8 h after synthesis. Proinsulin formed a concentrated patch detected by immunofluorescence in transfected cells that did not colocalize with calreticulin or BiP, markers for the endoplasmic reticulum, but did colocalize with membrin, a marker for the cis-medial Golgi complex. Proinsulin formed a Lubrol-insoluble aggregate within 30 min after synthesis in non-beta-cells but not in INS-1E cells, a beta-cell line that normally produces insulin. More than 45% of (35)S-HB10D proinsulin was secreted from COS cells 3 h after synthesis, and this mutant formed less Lubrol-insoluble aggregate in the cells than did wild-type hormone. These results indicate that proinsulin production from these non-beta-cells is not efficient and that proinsulin aggregates in their secretory pathways. Factors in the environment of the secretory pathway of beta-cells may prevent aggregation of proinsulin to allow efficient production.

  17. Sodium hydroxide catalyzed monodispersed high surface area silica nanoparticles.

    PubMed

    Bhakta, Snehasis; Dixit, Chandra K; Bist, Itti; Jalil, Karim Abdel; Suib, Steven L; Rusling, James F

    2016-07-01

    Understanding of the synthesis kinetics and our ability to modulate medium conditions allowed us to generate nanoparticles via an ultra-fast process. The synthesis medium is kept quite simple with tetraethyl orthosilicate (TEOS) as precursor and 50% ethanol and sodium hydroxide catalyst. Synthesis is performed under gentle conditions at 20 °C for 20 min Long synthesis time and catalyst-associated drawbacks are most crucial in silica nanoparticle synthesis. We have addressed both these bottlenecks by replacing the conventional Stober catalyst, ammonium hydroxide, with sodium hydroxide. We have reduced the overall synthesis time from 20 to 1/3 h, ~60-fold decrease, and obtained highly monodispersed nanoparticles with 5-fold higher surface area than Stober particles. We have demonstrated that the developed NPs with ~3-fold higher silane can be used as efficient probes for biosensor applications.

  18. Catalytic chemical amide synthesis at room temperature: one more step toward peptide synthesis.

    PubMed

    Mohy El Dine, Tharwat; Erb, William; Berhault, Yohann; Rouden, Jacques; Blanchet, Jérôme

    2015-05-01

    An efficient method has been developed for direct amide bond synthesis between carboxylic acids and amines via (2-(thiophen-2-ylmethyl)phenyl)boronic acid as a highly active bench-stable catalyst. This catalyst was found to be very effective at room temperature for a large range of substrates with slightly higher temperatures required for challenging ones. This methodology can be applied to aliphatic, α-hydroxyl, aromatic, and heteroaromatic acids as well as primary, secondary, heterocyclic, and even functionalized amines. Notably, N-Boc-protected amino acids were successfully coupled in good yields with very little racemization. An example of catalytic dipeptide synthesis is reported.

  19. The effect of reactor geometry on the synthesis of graphene materials in plasma jets

    NASA Astrophysics Data System (ADS)

    Shavelkina, M. B.; Amirov, R. H.; Shatalova, T. B.

    2017-05-01

    The possibility of synthesis of graphene and graphane (hydrogenated graphene) using the decomposition of hydrocarbons by thermal plasma has been investigated. Investigations of the influence of the plasma-forming gas on the efficiency of synthesis and the morphology of graphene materials were carried out. The synthesis products have been characterized by the methods of scanning microscopy, Raman spectroscopy and thermal analysis. It is found that the morphology of graphene materials is affected by the geometry of the reactor. It was demonstrated that the obtained graphene materials are uniformly distributed in the volume of plastic based on cyanate ester resins under mixing.

  20. Use of the 2-chlorotrityl chloride resin for microwave-assisted solid phase peptide synthesis.

    PubMed

    Ieronymaki, Matthaia; Androutsou, Maria Eleni; Pantelia, Anna; Friligou, Irene; Crisp, Molly; High, Kirsty; Penkman, Kirsty; Gatos, Dimitrios; Tselios, Theodore

    2015-09-01

    A fast and efficient microwave (MW)-assisted solid-phase peptide synthesis protocol using the 2-chlorotrityl chloride resin and the Fmoc/tBu methodology, has been developed. The established protocol combines the advantages of MW irradiation and the acid labile 2-chlorotrityl chloride resin. The effect of temperature during the MW irradiation, the degree of resin substitution during the coupling of the first amino acids and the rate of racemization for each amino acid were evaluated. The suggested solid phase methodology is applicable for orthogonal peptide synthesis and for the synthesis of cyclic peptides. © 2015 Wiley Periodicals, Inc.

  1. The origin of polynucleotide-directed protein synthesis

    NASA Technical Reports Server (NTRS)

    Orgel, Leslie E.

    1989-01-01

    If protein synthesis evolved in an RNA world it was probably preceded by simpler processes by means of which interaction with amino acids conferred selective advantage on replicating RNA molecules. It is suggested that at first the simple attachment of amino acids to the 2'(3') termini of RNA templates favored initiation of replication at the end of the template rather than at internal positions. The second stage in the evolution of protein synthesis would probably have been the association of pairs of charged RNA adaptors in such a way as to favor noncoded formation of peptides. Only after this process had become efficient could coded synthesis have begun.

  2. Direct C-H Arylation Meets Perovskite Solar Cells: Sn-Free Synthesis Shortcut to High Performance Hole-Transporting Materials.

    PubMed

    Chang, Yu-Chieh; Lee, Kun-Mu; Lai, Chia-Hsin; Liu, Ching-Yuan

    2018-03-30

    In contrast to the traditional multistep synthesis, we demonstrate herein a two-step synthesis-shortcut to triphenylamine-based hole-transporting materials (HTMs) through sequential direct C-H arylations. These hole-transporting molecules are fabricated in perovskite-based solar cells (PSCs), exhibiting promising efficiencies up to 17.69%, which is comparable to PSCs utilizing the commercially available spiro-OMeTAD as HTM. This is the first report describing the use of step-saving C-H activations/arylations in the facile synthesis of small-molecule HTMs for perovskite solar cells. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Synthesizing alkali ferrates using a waste as a raw material

    NASA Astrophysics Data System (ADS)

    Kanari, N.; Ostrosi, E.; Ninane, L.; Neveux, N.; Evrard, O.

    2005-08-01

    This study focused on the potential to transform a waste, hydrated iron sulfate, into a useful product. The waste was generated from titanium dioxide production and from the surface treatment of steel. Its disposal is restricted by environmental regulations, and consequently, it has to be recycled and/or treated. The described recycling was achieved through synthesis of potassium ferrate, which contains iron in a hexavalent state (FeVI). The synthesis process was achieved in a rotary reactor at room temperature using chlorine as an oxidant. The efficiency of potassium ferrate synthesis was about 60%. This paper presents details of the kinetics of the potassium ferrate synthesis.

  4. Effect of preoperative antiplatelet drugs on vascular prostacyclin synthesis.

    PubMed

    Karwande, S V; Weksler, B B; Gay, W A; Subramanian, V A

    1987-03-01

    Patients undergoing aortocoronary bypass using autogenous saphenous veins were randomly divided into three comparable groups. Group 1 (n = 10) acted as a control, Group 2 (n = 14) received 80 mg of aspirin at midnight before the operation, and Group 3 (n = 12) received 80 mg of aspirin and 75 mg of dipyridamole at midnight and an additional 75-mg dose of dipyridamole at 6 AM. The purpose was to determine which regimen would maximally inhibit platelet function without depressing vascular prostacyclin synthesis. Serum thromboxane A2, saphenous vein wall and aortic wall prostacyclin, platelet aggregation, and bleeding time were measured in all patients. None was restarted on a regimen of aspirin or dipyridamole postoperatively. Aspirin alone and in combination with dipyridamole significantly inhibited thromboxane A2 and platelet aggregation in all treated patients but spared venous prostacyclin synthesis. Aortic prostacyclin synthesis was partially inhibited in both treated groups. Chest tube drainage was comparable in all three groups. These results indicate that the combination of aspirin and dipyridamole offers no measurable advantage over aspirin alone in the perioperative period.

  5. Quantum information and the problem of mechanisms of biological evolution.

    PubMed

    Melkikh, Alexey V

    2014-01-01

    One of the most important conditions for replication in early evolution is the de facto elimination of the conformational degrees of freedom of the replicators, the mechanisms of which remain unclear. In addition, realistic evolutionary timescales can be established based only on partially directed evolution, further complicating this issue. A division of the various evolutionary theories into two classes has been proposed based on the presence or absence of a priori information about the evolving system. A priori information plays a key role in solving problems in evolution. Here, a model of partially directed evolution, based on the learning automata theory, which includes a priori information about the fitness space, is proposed. A potential repository of such prior information is the states of biologically important molecules. Thus, the need for extended evolutionary synthesis is discussed. Experiments to test the hypothesis of partially directed evolution are proposed. Copyright © 2013 Elsevier Ireland Ltd. All rights reserved.

  6. Combining Partial Directed Coherence and Graph Theory to Analyse Effective Brain Networks of Different Mental Tasks.

    PubMed

    Huang, Dengfeng; Ren, Aifeng; Shang, Jing; Lei, Qiao; Zhang, Yun; Yin, Zhongliang; Li, Jun; von Deneen, Karen M; Huang, Liyu

    2016-01-01

    The aim of this study is to qualify the network properties of the brain networks between two different mental tasks (play task or rest task) in a healthy population. EEG signals were recorded from 19 healthy subjects when performing different mental tasks. Partial directed coherence (PDC) analysis, based on Granger causality (GC), was used to assess the effective brain networks during the different mental tasks. Moreover, the network measures, including degree, degree distribution, local and global efficiency in delta, theta, alpha, and beta rhythms were calculated and analyzed. The local efficiency is higher in the beta frequency and lower in the theta frequency during play task whereas the global efficiency is higher in the theta frequency and lower in the beta frequency in the rest task. This study reveals the network measures during different mental states and efficiency measures may be used as characteristic quantities for improvement in attentional performance.

  7. Iron Oxide-Supported Copper Oxide Nanoparticles (Nanocat-Fe-CuO): Magnetically Recyclable Catalysts for the Synthesis of Pyrazole Derivatives, 4-Methoxyaniline, and Ullmann-type Condensation Reactions

    EPA Science Inventory

    An efficient and benign protocol is reported for the synthesis of 4-methoxyaniline, medicinally important pyrazole derivatives, and Ullmann-type condensation reaction using magnetically separable and reusable magnetite-supported copper (nanocat-Fe-CuO) nanoparticles under mild co...

  8. Facile, eco-friendly, catalyst-free synthesis of polyfunctionalized quinoxalines.

    PubMed

    Zhang, Yaohong; Luo, Mengqiang; Li, Yan; Wang, Hai; Ren, Xiaorong; Qi, Chenze

    2018-02-01

    A novel, facile and eco-friendly synthesis of quinoxalines from [Formula: see text] and 1,2-diamines was developed. An attractive feature of this protocol is that the desired products could be generated efficiently in water and without any catalyst, which is in accordance with the aim of green chemistry. A plausible mechanism has been proposed.

  9. Nano-particulate Aluminium Nitride/Al: An Efficient and Versatile Heterogeneous Catalyst for the Synthesis of Biginelli Scaffolds

    NASA Astrophysics Data System (ADS)

    Tekale, S. U.; Tekale, A. B.; Kanhe, N. S.; Bhoraskar, S. V.; Pawar, R. P.

    2011-12-01

    Nano-particulate aluminium nitride/Al (7:1) is reported as a new heterogeneous solid acid catalyst for the synthesis of 3, 4-dihydroxypyrimidi-2-(1H)-ones and their sulphur analogues using the Biginelli reaction. This method involves short reaction time, easy separation, high yields and purity of products.

  10. GREEN AND CONTROLLED SYNTHESIS OF GOLD AND PLATINUM NANOMATERIALS USING VITAMIN B2: DENSITY-ASSISTED SELF-ASSEMBLY OF NANOSPHERES, WIRES AND RODS

    EPA Science Inventory

    For the first time, we report density-assisted self-assembly and efficient synthesis of gold (Au) and platinum (Pt) nanospheres, nanowires and nanorods using vitamin B2 (riboflavin) without employing any special capping or dispersing agent at room temperature; this env...

  11. A facile synthesis of substituted 2-alkylquinolines through [3+3] annulation between 3-ethoxycyclobutanones and aromatic amines at room temperature.

    PubMed

    Shan, Gang; Sun, Xiuyun; Xia, Qian; Rao, Yu

    2011-11-04

    An efficient single-step approach toward the synthesis of 2-alkylquinolines is described. Through a Lewis acid mediated [3+3] annulation reaction between 3-ethoxycyclobutanones and aromatic amines, a variety of multisubstituted 2-alkylquinoline derivatives were prepared regioselectively at room temperature. © 2011 American Chemical Society

  12. Nazarov cyclization initiated by peracid oxidation: the total synthesis of (+/-)-rocaglamide.

    PubMed

    Malona, John A; Cariou, Kevin; Frontier, Alison J

    2009-06-10

    The total syntheses of aglafolin, rocagloic acid, and rocaglamide using Nazarov cyclization are described. Generation of the necessary oxyallyl cation intermediate was accomplished via peracid oxidation of an allenol ether to generate an unusual oxycarbenium ion species that undergoes cyclization. The synthesis is efficient, highly diastereoselective, and strategically distinct from previous syntheses of rocaglamide.

  13. Synthesis of 2-Ethenylcyclopropyl Aryl Ketones via Intramolecular SN2-like Displacement of an Ester.

    PubMed

    Jung, Michael E; Sun, Daniel L; Dwight, Timothy A; Yu, Peiyuan; Li, Wei; Houk, K N

    2016-10-07

    The efficient synthesis of trans-2-ethenylcyclopropyl aryl ketones via an intramolecular S N 2-like displacement of an allylic ester is reported. A novel 1,5-acyl shift process is also observed that contributes to the product mixture. Theoretical calculations provide a rationale for the observed product ratio.

  14. Direct synthesis of alkenyl iodides via indium-catalyzed iodoalkylation of alkynes with alcohols and aqueous HI.

    PubMed

    Wu, Chao; Wang, Zheng; Hu, Zhan; Zeng, Fei; Zhang, Xing-Yu; Cao, Zhong; Tang, Zilong; He, Wei-Min; Xu, Xin-Hua

    2018-05-02

    A convenient and efficient indium-catalyzed approach to synthesize alkenyl iodides has been developed through direct iodoalkylation of alkynes with alcohols and aqueous HI under mild conditions. This catalytic protocol offers an attractive approach for the synthesis of a diverse range of alkenyl iodides in good to excellent yields.

  15. Synthesis of functionalized chromenes from Meldrum's acid, 4-hydroxycoumarin, and ketones or aldehydes.

    PubMed

    Sabbaghan, Maryam; Yavari, Issa; Hossaini, Zinatossadat

    2010-11-01

    An efficient synthesis of 4-alkyl-4-methyl-3,4-dihydro-2H,5H-pyrano[3,2-c]chromene-2,5-dione or 4-aryl-3,4-dihydro-2H,5H-pyrano[3,2-c]chromene-2,5-diones via reaction 4-hydroxycoumarin with Meldrum's acid and ketones or aldehydes is described.

  16. Flow cytometric measurement of total DNA and incorporated halodeoxyuridine

    DOEpatents

    Dolbeare, F.A.; Gray, J.W.

    1983-10-18

    A method for the simultaneous flow cylometric measurement of total cellular DNA content and of the uptake of DNA precursors as a measure of DNA synthesis during various phases of the cell cycle in normal and malignant cells in vitro and in vivo is described. The method comprises reacting cells with labelled halodeoxyuridine (HdU), partially denaturing cellular DNA, adding to the reaction medium monoclonal antibodies (mabs) reactive with HdU, reacting the bound mabs with a second labelled antibody, incubating the mixture with a DNA stain, and measuring simultaneously the intensity of the DNA stain as a measure of the total cellular DNA and the HdU incorporated as a measure of DNA synthesis. (ACR)

  17. The role of nickel in urea assimilation by algae.

    PubMed

    Rees, T A; Bekheet, I A

    1982-12-01

    Nickel is required for urease synthesis by Phaeodactylum tricornutum and Tetraselmis subcordiformis and for growth on urea by Phaeodactylum. There is no requirement for nickel for urea amidolyase synthesis by Chlorella fusca var. vacuolata. Neither copper nor palladium can substitute for nickel but cobalt partially restored urease activity in Phaeodactylum. The addition of nickel to nickel-deficient cultures of Phaeodactylum or Tetraselmis resulted in a rapid increase of urease activity to 7-30 times the normal level; this increase was not inhibited by cycloheximide. It is concluded that nickel-deficient cells over-produce a non-functional urease protein and that either nickel or the functional urease enzyme participates in the regulation of the production of urease protein.

  18. Chemical synthesis of 2',5'-oligoribonucleotides.

    PubMed

    Hirao, I; Nishino, S; Kamaike, K; Nishiyama, S; Ueda, S; Yamamoto, H; Ishido, Y

    1983-01-01

    Partial phenylcarbamoylation of ribonucleosides by metal carboxylates - phenyl isocyanate system was found to be induced at 2'-position with high regioselectivity in good yields, similar to that by amines - phenyl isocyanate system; these results prompted us to perform synthesis of oligoribonucleotides bearing 2'-5' phosphodiester linkage starting either from 5'-0-acetyl-2'-0-phenylcarbamoyl or from 2', 5'-bis(phenylcarbamo)yl derivatives through the sequence of reactions, i.e. tetrahydropyranylation at 3'-position, decarbamoylation and deacylation with sodium methoxide in methanol both at 2'- and 5'-positions, dimethoxytritylation at 5'-position, and phosphorylation at 2'-position with 5-chloro-8-quinolylphosphate/8-quinolinesulfonyl chloride, followed by the usual coupling procedures by Takaku et al).

  19. Solid-state combustion synthesis of ceramics and alloys in reduced gravity

    NASA Technical Reports Server (NTRS)

    Valone, S. M.; Behrens, R. G.

    1988-01-01

    Possible microgravity effects are explored in the combustion synthesis of ceramics and alloys from their constituent elements. Molten intermediates are typically present during the combustion process, thereby offering the chance for natural convection to take place. Numerical simulations suggest that the combustion front in concert with gravity may act as a partial zone-refinement mechanism which is attempting to sweep out porosity in the sample. Contrary to suggestions by dimensional analysis, no effects on the combustion rate are seen. An analytical model of the combustion velocity as a function of the gravitational field and the spreading rate of molten material gives the correct order of magnitude of the gravity effect as measured by centrifuge experiments.

  20. Engineering cyanogen synthesis and turnover in cassava (Manihot esculenta).

    PubMed

    Siritunga, Dimuth; Sayre, Richard

    2004-11-01

    Cassava is the major root crop for a quarter billion subsistence farmers in sub-Saharan Africa. It is valued for its ability to grow in adverse environments and the food security it provides. Cassava contains potentially toxic levels of cyanogenic glycosides (linamarin) which protect the plant from herbivory and theft. The cyanogens, including linamarin and its deglycosylated product, acetone cyanohydrin, can be efficiently removed from the root by various processing procedures. Short-cuts in processing, which may occur during famines, can result in only partial removal of cyanogens. Residual cyanogens in cassava foods may cause neurological disorders or paralysis, particularly in nutritionally compromised individuals. To address this problem and to further understand the function of cyanogenic glycosides in cassava, we have generated transgenic cassava in which cyanogenic glycoside synthesis has been selectively inhibited in leaves and roots by antisense expression of CYP79D1/D2 gene fragments. The CYP79D1/D2 genes encode two highly similar cytochrome P450s that catalyze the first-dedicated step in cyanogenic glycoside synthesis. Transgenic plants in which the expression of these genes was selectively inhibited in leaves had substantially reduced (60- 94% reduction) linamarin leaf levels. Surprisingly, these plants also had a greater than a 99% reduction in root linamarin content. In contrast, transgenic plants in which the CYP79D1/D2 transcripts were reduced to non-detectable levels in roots had normal root linamarin levels. These results demonstrate that linamarin synthesized in leaves is transported to the roots and accounts for nearly all of the root linamarin content. Importantly, transgenic plants having reduced leaf and root linamarin content were unable to grow in the absence of reduced nitrogen (NH3) . Cassava roots have previously been demonstrated to have an active cyanide assimilation pathway leading to the synthesis of amino acids. We propose that cyanide derived from linamarin is a major source of reduced nitrogen for cassava root protein synthesis. Disruption of linamarin transport from leaves in CYP79D1/D2 anti-sense plants prevents the growth of cassava roots in the absence of an alternate source of reduced nitrogen. An alternative strategy for reducing cyanogen toxicity in cassava foods is to accelerate cyanogenesis and cyanide volatilization during food processing. To achieve this objective, we have expressed the leaf-specific enzyme hydroxynitrile lyase (HNL) in roots. HNL catalyzes the breakdown of acetone cyanohydrin to cyanide. Expression of HNL in roots accelerated cyanogenesis by more than three-fold substantially reducing the accumulation of acetone cyanohydrin during processing relative to wild-type roots.

Top