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Sample records for abiotic organic synthesis

  1. Nitrogen isotopic fractionation during abiotic synthesis of organic solid particles

    CERN Document Server

    Kuga, Maïa; Marty, Bernard; Marrocchi, Yves; Bernard, Sylvain; Rigaudier, Thomas; Fleury, Benjamin; Tissandier, Laurent

    2014-01-01

    The formation of organic compounds is generally assumed to result from abiotic processes in the Solar System, with the exception of biogenic organics on Earth. Nitrogen-bearing organics are of particular interest, notably for prebiotic perspectives but also for overall comprehension of organic formation in the young solar system and in planetary atmospheres. We have investigated abiotic synthesis of organics upon plasma discharge, with special attention to N isotope fractionation. Organic aerosols were synthesized from N2-CH4 and N2-CO gaseous mixtures using low-pressure plasma discharge experiments, aimed at simulating chemistry occurring in Titan s atmosphere and in the protosolar nebula, respectively. Nitrogen is efficiently incorporated into the synthesized solids, independently of the oxidation degree, of the N2 content of the starting gas mixture, and of the nitrogen speciation in the aerosols. The aerosols are depleted in 15N by 15-25 permil relative to the initial N2 gas, whatever the experimental set...

  2. Pathways for abiotic organic synthesis at submarine hydrothermal fields.

    Science.gov (United States)

    McDermott, Jill M; Seewald, Jeffrey S; German, Christopher R; Sylva, Sean P

    2015-06-23

    Arguments for an abiotic origin of low-molecular weight organic compounds in deep-sea hot springs are compelling owing to implications for the sustenance of deep biosphere microbial communities and their potential role in the origin of life. Theory predicts that warm H2-rich fluids, like those emanating from serpentinizing hydrothermal systems, create a favorable thermodynamic drive for the abiotic generation of organic compounds from inorganic precursors. Here, we constrain two distinct reaction pathways for abiotic organic synthesis in the natural environment at the Von Damm hydrothermal field and delineate spatially where inorganic carbon is converted into bioavailable reduced carbon. We reveal that carbon transformation reactions in a single system can progress over hours, days, and up to thousands of years. Previous studies have suggested that CH4 and higher hydrocarbons in ultramafic hydrothermal systems were dependent on H2 generation during active serpentinization. Rather, our results indicate that CH4 found in vent fluids is formed in H2-rich fluid inclusions, and higher n-alkanes may likely be derived from the same source. This finding implies that, in contrast with current paradigms, these compounds may form independently of actively circulating serpentinizing fluids in ultramafic-influenced systems. Conversely, widespread production of formate by ΣCO2 reduction at Von Damm occurs rapidly during shallow subsurface mixing of the same fluids, which may support anaerobic methanogenesis. Our finding of abiogenic formate in deep-sea hot springs has significant implications for microbial life strategies in the present-day deep biosphere as well as early life on Earth and beyond.

  3. Evaluating reaction pathways of hydrothermal abiotic organic synthesis at elevated temperatures and pressures using carbon isotopes

    Science.gov (United States)

    Fu, Qi; Socki, Richard A.; Niles, Paul B.

    2015-04-01

    Experiments were performed to better understand the role of environmental factors on reaction pathways and corresponding carbon isotope fractionations during abiotic hydrothermal synthesis of organic compounds using piston cylinder apparatus at 750 °C and 5.5 kbars. Chemical compositions of experimental products and corresponding carbon isotopic values were obtained by a Pyrolysis-GC-MS-IRMS system. Alkanes (methane and ethane), straight-chain saturated alcohols (ethanol and n-butanol) and monocarboxylic acids (formic and acetic acids) were generated with ethanol being the only organic compound with higher δ13C than CO2. CO was not detected in experimental products owing to the favorable water-gas shift reaction under high water pressure conditions. The pattern of δ13C values of CO2, carboxylic acids and alkanes are consistent with their equilibrium isotope relationships: CO2 > carboxylic acids > alkanes, but the magnitude of the fractionation among them is higher than predicted isotope equilibrium values. In particular, the isotopic fractionation between CO2 and CH4 remained constant at ∼31‰, indicating a kinetic effect during CO2 reduction processes. No "isotope reversal" of δ13C values for alkanes or carboxylic acids was observed, which indicates a different reaction pathway than what is typically observed during Fischer-Tropsch synthesis under gas phase conditions. Under constraints imposed in experiments, the anomalous 13C isotope enrichment in ethanol suggests that hydroxymethylene is the organic intermediate, and that the generation of other organic compounds enriched in 12C were facilitated by subsequent Rayleigh fractionation of hydroxymethylene reacting with H2 and/or H2O. Carbon isotope fractionation data obtained in this study are instrumental in assessing the controlling factors on abiotic formation of organic compounds in hydrothermal systems. Knowledge on how environmental conditions affect reaction pathways of abiotic synthesis of organic

  4. Deep Carbon Cycling in the Deep Hydrosphere: Abiotic Organic Synthesis and Biogeochemical Cycling

    Science.gov (United States)

    Sherwood Lollar, B.; Sutcliffe, C. N.; Ballentine, C. J.; Warr, O.; Li, L.; Ono, S.; Wang, D. T.

    2014-12-01

    Research into the deep carbon cycle has expanded our understanding of the depth and extent of abiotic organic synthesis in the deep Earth beyond the hydrothermal vents of the deep ocean floor, and of the role of reduced gases in supporting deep subsurface microbial communities. Most recently, this research has expanded our understanding not only of the deep biosphere but the deep hydrosphere - identifying for the first time the extreme antiquity (millions to billions of years residence time) of deep saline fracture waters in the world's oldest rocks. Energy-rich saline fracture waters in the Precambrian crust that makes up more than 70% of the Earth's continental lithosphereprovide important constraints on our understanding of the extent of the crust that is habitable, on the time scales of hydrogeologic isolation (and conversely mixing) of fluids relevant to the deep carbon cycle, and on the geochemistry of substrates that sustain both abiotic organic synthesis and biogeochemical cycles driven by microbial communities. Ultimately the chemistry and hydrogeology of the deep hydrosphere will help define the limits for life in the subsurface and the boundary between the biotic-abiotic fringe. Using a variety of novel techniques including noble gas analysis, clumped isotopologues of methane, and compound specific isotope analysis of CHNOS, this research is addressing questions about the distribution of deep saline fluids in Precambrian rocks worldwide, the degree of interconnectedness of these potential biomes, the habitability of these fluids, and the biogeographic diversity of this new realm of the deep hydrosphere.

  5. Carbon Isotopes of Alkanes in Hydrothermal Abiotic Organic Synthesis Processes at High Temperatures and Pressures: An Experimental Study

    Science.gov (United States)

    Fu, Qi; Socki, Richard A.; Niles, Paul B.

    2010-01-01

    Observation of methane in the Martian atmosphere has been reported by different detection techniques [1-4]. With more evidence showing extensive water-rock interaction in Martian history [5-7], abiotic formation by Fischer-Tropsch Type (FTT) synthesis during serpentization reactions may be one possible process responsible for methane generation on Mars [8, 9]. While the experimental studies performed to date leave little doubt that chemical reactions exist for the abiotic synthesis of organic compounds by mineral surface-catalyzed reactions [10-12], little is known about the reaction pathways by which CO2 and/or CO are reduced under hydrothermal conditions. Carbon and hydrogen isotope measurements of alkanes have been used as an effective tool to constrain the origin and reaction pathways of hydrocarbon formation. Alkanes generated by thermal breakdown of high molecular weight organic compounds have carbon and hydrogen isotopic signatures completely distinct from those formed abiotically [13-15]. Recent experimental studies, however, showed that different abiogenic hydrocarbon formation processes (e.g., polymerization vs. depolymerization) may have different carbon and hydrogen isotopic patterns [16]. Results from previous experiments studying decomposition of higher molecular weight organic compounds (lignite) also suggested that pressure could be a crucial factor affecting fractionation of carbon isotopes [17]. Under high pressure conditions, no experimental data are available describing fractionation of carbon isotope during mineral catalyzed FTT synthesis. Thus, hydrothermal experiments present an excellent opportunity to provide the requisite carbon isotope data. Such data can also be used to identify reaction pathways of abiotic organic synthesis under experimental conditions.

  6. Reduction of nitrogen compounds in oceanic basement and its implications for HCN formation and abiotic organic synthesis

    Directory of Open Access Journals (Sweden)

    Neubeck Anna

    2009-10-01

    Full Text Available Abstract Hydrogen cyanide is an excellent organic reagent and is central to most of the reaction pathways leading to abiotic formation of simple organic compounds containing nitrogen, such as amino acids, purines and pyrimidines. Reduced carbon and nitrogen precursor compounds for the synthesis of HCN may be formed under off-axis hydrothermal conditions in oceanic lithosphere in the presence of native Fe and Ni and are adsorbed on authigenic layer silicates and zeolites. The native metals as well as the molecular hydrogen reducing CO2 to CO/CH4 and NO3-/NO2- to NH3/NH4+ are a result of serpentinization of mafic rocks. Oceanic plates are conveyor belts of reduced carbon and nitrogen compounds from the off-axis hydrothermal environments to the subduction zones, where compaction, dehydration, desiccation and diagenetic reactions affect the organic precursors. CO/CH4 and NH3/NH4+ in fluids distilled out of layer silicates and zeolites in the subducting plate at an early stage of subduction will react upon heating and form HCN, which is then available for further organic reactions to, for instance, carbohydrates, nucleosides or even nucleotides, under alkaline conditions in hydrated mantle rocks of the overriding plate. Convergent margins in the initial phase of subduction must, therefore, be considered the most potent sites for prebiotic reactions on Earth. This means that origin of life processes are, perhaps, only possible on planets where some kind of plate tectonics occur.

  7. Reduction of nitrogen compounds in oceanic basement and its implications for HCN formation and abiotic organic synthesis.

    Science.gov (United States)

    Holm, Nils G; Neubeck, Anna

    2009-01-01

    Hydrogen cyanide is an excellent organic reagent and is central to most of the reaction pathways leading to abiotic formation of simple organic compounds containing nitrogen, such as amino acids, purines and pyrimidines. Reduced carbon and nitrogen precursor compounds for the synthesis of HCN may be formed under off-axis hydrothermal conditions in oceanic lithosphere in the presence of native Fe and Ni and are adsorbed on authigenic layer silicates and zeolites. The native metals as well as the molecular hydrogen reducing CO2 to CO/CH4 and NO3-/NO2- to NH3/NH4+ are a result of serpentinization of mafic rocks. Oceanic plates are conveyor belts of reduced carbon and nitrogen compounds from the off-axis hydrothermal environments to the subduction zones, where compaction, dehydration, desiccation and diagenetic reactions affect the organic precursors. CO/CH4 and NH3/NH4+ in fluids distilled out of layer silicates and zeolites in the subducting plate at an early stage of subduction will react upon heating and form HCN, which is then available for further organic reactions to, for instance, carbohydrates, nucleosides or even nucleotides, under alkaline conditions in hydrated mantle rocks of the overriding plate. Convergent margins in the initial phase of subduction must, therefore, be considered the most potent sites for prebiotic reactions on Earth. This means that origin of life processes are, perhaps, only possible on planets where some kind of plate tectonics occur. PMID:19849830

  8. Experimental Study of Abiotic Organic Synthesis at High Temperature and Pressure Conditions: Carbon Isotope and Mineral Surface Characterizations

    Science.gov (United States)

    Fu, Qi; Socki, R. A.; Niles, P. B.

    2010-01-01

    Abiotic organic synthesis processes have been proposed as potential mechanisms for methane generation in subseafloor hydrothermal systems on Earth, and on other planets. To better understand the detailed reaction pathways and carbon isotope fractionations in this process under a wide range of physical and chemical conditions, hydrothermal experiments at high temperature (750 C) and pressure (0.55 GPa) were performed using piston cylinder apparatus. Formic acid was used as the source of CO2 and H2, and magnetite was the mineral catalyst. The chemical and carbon isotopic compositions of dissolved organic products were determined by GC-C-MS-IRMS, while organic intermediaries on the mineral catalyst were characterized by Pyrolysis-GC-MS. Among experimental products, dissolved CO2 was the dominant carbon species with a relative abundance of 88 mol%. Dissolved CH4 and C2H6 were also identified with a mole ratio of CH4 over C2H6 of 15:1. No dissolved CO was detected in the experiment, which might be attributable to the loss of H2 through the Au capsule used in the experiments at high temperature and pressure conditions and corresponding conversion of CO to CO2 by the water-gas shift reaction. Carbon isotope results showed that the 13C values of CH4 and C2H6 were -50.3% and -39.3% (V-PDB), respectively. CO2 derived from decarboxylation of formic acid had a (sigma)C-13 value of -19.2%, which was 3.2% heavier than its source, formic acid. The (sigma)C-13 difference between CO2 and CH4 was 31.1%, which was higher than the value of 9.4% calculated from theoretical isotopic equilibrium predictions at experimental conditions, suggesting the presence of a kinetic isotope effect. This number was also higher than the values (4.6 to 27.1%) observed in similar experiments previously performed at 400 C and 50 MPa with longer reaction times. CH4 is 11.0% less enriched in C-13 than C2H6. Alcohols were observed as carbon compounds on magnetite surfaces by Pyrolysis-GC-MS, which confirms

  9. Abiotic Bromination of Soil Organic Matter.

    Science.gov (United States)

    Leri, Alessandra C; Ravel, Bruce

    2015-11-17

    Biogeochemical transformations of plant-derived soil organic matter (SOM) involve complex abiotic and microbially mediated reactions. One such reaction is halogenation, which occurs naturally in the soil environment and has been associated with enzymatic activity of decomposer organisms. Building on a recent finding that naturally produced organobromine is ubiquitous in SOM, we hypothesized that inorganic bromide could be subject to abiotic oxidations resulting in bromination of SOM. Through lab-based degradation treatments of plant material and soil humus, we have shown that abiotic bromination of particulate organic matter occurs in the presence of a range of inorganic oxidants, including hydrogen peroxide and assorted forms of ferric iron, producing both aliphatic and aromatic forms of organobromine. Bromination of oak and pine litter is limited primarily by bromide concentration. Fresh plant material is more susceptible to bromination than decayed litter and soil humus, due to a labile pool of mainly aliphatic compounds that break down during early stages of SOM formation. As the first evidence of abiotic bromination of particulate SOM, this study identifies a mechanistic source of the natural organobromine in humic substances and the soil organic horizon. Formation of organobromine through oxidative treatments of plant material also provides insights into the relative stability of aromatic and aliphatic components of SOM.

  10. Hydrothermal organic synthesis experiments

    Science.gov (United States)

    Shock, Everett L.

    1992-01-01

    Ways in which heat is useful in organic synthesis experiments are described, and experiments on the hydrothermal destruction and synthesis of organic compounds are discussed. It is pointed out that, if heat can overcome kinetic barriers to the formation of metastable states from reduced or oxidized starting materials, abiotic synthesis under hydrothermal conditions is a distinct possibility. However, carefully controlled experiments which replicate the descriptive variables of natural hydrothermal systems have not yet been conducted with the aim of testing the hypothesis of hydrothermal organic systems.

  11. Organic Synthesis

    OpenAIRE

    Romea, Pedro

    2014-01-01

    Organic Synthesis is a one-semester course of the fourth year of the Chemistry Degree at the Universitat de Barcelona. This course covers the most important transformations in Organic Chemistry, including a short introduction to the Retrosynthetic Analysis. The aim is to provide a solid knowledge of the main reactions and their mechanism, which could later be improved during Master studies.

  12. Hydrothermal organic synthesis experiments

    Science.gov (United States)

    Shock, Everett L.

    1992-01-01

    The serious scientific debate about spontaneous generation which raged for centuries reached a climax in the nineteenth century with the work of Spallanzani, Schwann, Tyndall, and Pasteur. These investigators demonstrated that spontaneous generation from dead organic matter does not occur. Although no aspects of these experiments addressed the issue of whether organic compounds could be synthesized abiotically, the impact of the experiments was great enough to cause many investigators to assume that life and its organic compounds were somehow fundamentally different than inorganic compounds. Meanwhile, other nineteenth-century investigators were showing that organic compounds could indeed be synthesized from inorganic compounds. In 1828 Friedrich Wohler synthesized urea in an attempt to form ammonium cyanate by heating a solution containing ammonia and cyanic acid. This experiment is generally recognized to be the first to bridge the artificial gap between organic and inorganic chemistry, but it also showed the usefulness of heat in organic synthesis. Not only does an increase in temperature enhance the rate of urea synthesis, but Walker and Hambly showed that equilibrium between urea and ammonium cyanate was attainable and reversible at 100 C. Wohler's synthesis of urea, and subsequent syntheses of organic compounds from inorganic compounds over the next several decades dealt serious blows to the 'vital force' concept which held that: (1) organic compounds owe their formation to the action of a special force in living organisms; and (2) forces which determine the behavior of inorganic compounds play no part in living systems. Nevertheless, such progress was overshadowed by Pasteur's refutation of spontaneous generation which nearly extinguished experimental investigations into the origins of life for several decades. Vitalism was dealt a deadly blow in the 1950's with Miller's famous spark-discharge experiments which were undertaken in the framework of the Oparin

  13. Abiotic stress modifies the synthesis of alpha-tocopherol and beta-carotene in phytoplankton species.

    Science.gov (United States)

    Häubner, Norbert; Sylvander, Peter; Vuori, Kristiina; Snoeijs, Pauline

    2014-08-01

    We performed laboratory experiments to investi-gate whether the synthesis of the antioxidants α-tocopherol (vitamin E) and β-carotene in phytoplankton depends on changes in abiotic factors. Cultures of Nodularia spumigena, Phaeodactylum tricornutum, Skeletonema costatum, Dunaliella tertiolecta, Prorocentrum cordatum, and Rhodomonas salina were incubated at different tempe-ratures, photon flux densities and salinities for 48 h. We found that abiotic stress, within natural ecological ranges, affects the synthesis of the two antioxidants in different ways in different species. In most cases antioxidant production was stimulated by increased abiotic stress. In P. tricornutum KAC 37 and D. tertiolecta SCCAP K-0591, both good producers of this compound, α-tocopherol accumulation was negatively affected by environmentally induced higher photosystem II efficiency (Fv /Fm ). On the other hand, β-carotene accumulation was positively affected by higher Fv /Fm in N. spumigena KAC 7, P. tricornutum KAC 37, D. tertiolecta SCCAP K-0591 and R. salina SCCAP K-0294. These different patterns in the synthesis of the two compounds may be explained by their different locations and functions in the cell. While α-tocopherol is heavily involved in the protection of prevention of lipid peroxidation in membranes, β-carotene performs immediate photo-oxidative protection in the antennae complex of photosystem II. Overall, our results suggest a high variability in the antioxidant pool of natural aquatic ecosystems, which can be subject to short-term temperature, photon flux density and salinity fluctuations. The antioxidant levels in natural phytoplankton communities depend on species composition, the physiological condition of the species, and their respective strategies to deal with reactive oxygen species. Since α-tocopherol and β-carotene, as well as many other nonenzymatic antioxidants, are exclusively produced by photo-synthetic organisms, and are required by higher

  14. Thermodynamic Potential for the Abiotic Synthesis of Adenine, Cytosine, Guanine, Thymine, Uracil, Ribose, and Deoxyribose in Hydrothermal Systems

    NARCIS (Netherlands)

    LaRowe, D.E.; Regnier, P.

    2008-01-01

    The thermodynamic potential for the abiotic synthesis of the five common nucleobases (adenine, cytosine, guanine, thymine, and uracil) and two monosaccharides (ribose and deoxyribose) from formaldehyde and hydrogen cyanide has been quantified under temperature, pressure, and bulk composition conditi

  15. Induction of Glutathione Synthesis and Glutathione Reductase Activity by Abiotic Stresses in Maize and Wheat

    OpenAIRE

    Gabor Kocsy; Gabriella Szalai; Gabor Galiba

    2002-01-01

    The effect of different abiotic stresses (extreme temperatures and osmotic stress) on the synthesis of glutathione and hydroxymethylglutathione, on the ratio of the reduced to oxidised forms of these thiols (GSH/GSSG, hmGSH/hmGSSG), and on the glutathione reductase (GR) activity was studied in maize and wheat genotypes having different sensitivity to low temperature stress. Cold treatment induced a greater increase in total glutathione (TG) content and in GR activity in tolerant genotypes of ...

  16. Thermodynamic potential for the abiotic synthesis of Adenine, Cytosine, Guanine, Thymine, Uracil, Ribose, and Deoxyribose in hydrothermal systems

    OpenAIRE

    Larowe, D. E.; Regnier, P.

    2008-01-01

    The thermodynamic potential for the abiotic synthesis of the five common nucleobases (adenine, cytosine, guanine, thymine, and uracil) and two monosaccharides (ribose and deoxyribose) from formaldehyde and hydrogen cyanide has been quantified under temperature, pressure, and bulk composition conditions that are representative of hydrothermal systems. The activities of the precursor molecules (formaldehyde and hydrogen cyanide) required to evaluate the thermodynamics of biomolecule synthesis w...

  17. Aerobic bacterial catabolism of persistent organic pollutants - potential impact of biotic and abiotic interaction.

    Science.gov (United States)

    Jeon, Jong-Rok; Murugesan, Kumarasamy; Baldrian, Petr; Schmidt, Stefan; Chang, Yoon-Seok

    2016-04-01

    Several aerobic bacteria possess unique catabolic pathways enabling them to degrade persistent organic pollutants (POPs), including polychlorinated dibenzo-p-dioxins/furans (PCDD/Fs), polybrominated diphenylethers (PBDEs), and polychlorinated biphenyls (PCBs). The catabolic activity of aerobic bacteria employed for removal of POPs in the environment may be modulated by several biotic (i.e. fungi, plants, algae, earthworms, and other bacteria) and abiotic (i.e. zero-valent iron, advanced oxidation, and electricity) agents. This review describes the basic biochemistry of the aerobic bacterial catabolism of selected POPs and discusses how biotic and abiotic agents enhance or inhibit the process. Solutions allowing biotic and abiotic agents to exert physical and chemical assistance to aerobic bacterial catabolism of POPs are also discussed. PMID:26851837

  18. Aerobic bacterial catabolism of persistent organic pollutants - potential impact of biotic and abiotic interaction.

    Science.gov (United States)

    Jeon, Jong-Rok; Murugesan, Kumarasamy; Baldrian, Petr; Schmidt, Stefan; Chang, Yoon-Seok

    2016-04-01

    Several aerobic bacteria possess unique catabolic pathways enabling them to degrade persistent organic pollutants (POPs), including polychlorinated dibenzo-p-dioxins/furans (PCDD/Fs), polybrominated diphenylethers (PBDEs), and polychlorinated biphenyls (PCBs). The catabolic activity of aerobic bacteria employed for removal of POPs in the environment may be modulated by several biotic (i.e. fungi, plants, algae, earthworms, and other bacteria) and abiotic (i.e. zero-valent iron, advanced oxidation, and electricity) agents. This review describes the basic biochemistry of the aerobic bacterial catabolism of selected POPs and discusses how biotic and abiotic agents enhance or inhibit the process. Solutions allowing biotic and abiotic agents to exert physical and chemical assistance to aerobic bacterial catabolism of POPs are also discussed.

  19. Coupled biotic-abiotic oxidation of organic matter by biogenic MnO_{2}

    Science.gov (United States)

    Gonzalez, Julia; Peña, Jasquelin

    2016-04-01

    Some reactive soil minerals are strongly implicated in stabilising organic matter. However, others can play an active role in the oxidation of organic molecules. In natural systems, layer-type manganese oxide minerals (MnO2) typically occur as biomineral assemblages consisting of mineral particles and microbial biomass. Both the mineral and biological fractions of the assemblage can be powerful oxidants of organic C. The biological compartment relies on a set of enzymes to drive oxidative transformations of reduced C-substrates, whereas MnO2 minerals are strong, less specific abiotic oxidants that are assumed to rely on interfacial interactions between C-substrates and the mineral surface. This project aims to understand the coupling between microbial C mineralization and abiotic C oxidation mediated by MnO2 in bacterial-MnO2 assemblages. Specifically, under conditions of high C turnover, microbial respiration can significantly alter local pH, dissolved oxygen and pool of available reductants, which may modify rates and mechanism of C oxidation by biotic and abiotic components. We first investigated changes in the solution chemistry of Pseudomonas putida suspensions exposed to varying concentrations of glucose, chosen to represent readily bioavailable substrates in soils. Glucose concentrations tested ranged between 0 and 5.5mM and changes in pH, dissolved oxygen and dissolved organic and inorganic carbon were tracked over 48h. We then combined literature review and wet-chemical experiments to compile the pH dependence of rates of organic substrate oxidation by MnO2, including glucose. Our results demonstrate a strong pH dependence for these abiotic reactions. In assemblages of P. putida - MnO2, kinetic limitations for abiotic C oxidation by MnO2 are overcome by changes in biogeochemical conditions that result from bacterial C metabolism. When extrapolated to a soil solution confronted to an input of fresh dissolved organic matter, bacterial C metabolism of the

  20. Organic Synthesis in Space

    Science.gov (United States)

    Sandford, Scott A.; DeVincenzi, Donald (Technical Monitor)

    2002-01-01

    This talk will review our current understanding of the synthesis of organic molecules in space, with particular emphasis on the synthesis of those compounds that may be of prebiotic interest. The talk will address the possibility that molecules created in the interstellar medium may play a role in the origin and evolution of life on planetary surfaces. The various organic and volatile compounds that are now known or suspected to exist in a variety of space environments (stellar outflows, the diffuse interstellar medium, dense molecular clouds, protostellar nebulae, and planetesimal parent bodies in planetary systems) will be reviewed. This information comes largely from the combined applications of observational infrared and radio spectroscopy, laboratory astrophysical simulations, and theoretical astrochemistry. This will be followed by a discussion of the evidence, largely gathered from the laboratory isotopic study of extraterrestrial materials (meteorites and cosmic dust), that interstellar materials, including organics, can and do survive the transition from the interstellar space into forming stellar systems. Once there, some of this material can be delivered largely unaltered to planetary surfaces where it can play key roles in the origin and subsequent evolution of life.

  1. Abiotic origin of biopolymers

    Science.gov (United States)

    Oro, J.; Stephen-Sherwood, E.

    1976-01-01

    A variety of methods have been investigated in different laboratories for the polymerization of amino acids and nucleotides under abiotic conditions. They include (1) thermal polymerization; (2) direct polymerization of certain amino acid nitriles, amides, or esters; (3) polymerization using polyphosphate esters; (4) polymerization under aqueous or drying conditions at moderate temperatures using a variety of simple catalysts or condensing agents like cyanamide, dicyandiamide, or imidazole; and (5) polymerization under similar mild conditions but employing activated monomers or abiotically synthesized high-energy compounds such as adenosine 5'-triphosphate (ATP). The role and significance of these methods for the synthesis of oligopeptides and oligonucleotides under possible primitive-earth conditions is evaluated. It is concluded that the more recent approach involving chemical processes similar to those used by contemporary living organisms appears to offer a reasonable solution to the prebiotic synthesis of these biopolymers.

  2. Abiotic reduction reactions of anthropogenic organic chemicals in anaerobic systems: A critical review

    Science.gov (United States)

    Macalady, Donald L.; Tratnyek, Paul G.; Grundl, Timothy J.

    1986-02-01

    This review is predicated upon the need for a detailed process-level understanding of factors influencing the reduction of anthropogenic organic chemicals in natural aquatic systems. In particular, abiotic reductions of anthropogenic organic chemicals are reviewed. The most important reductive reaction is alkyl dehalogenation (replacement of chloride with hydrogen) which occurs in organisms, sediments, sewage sludge, and reduced iron porphyrin model systems. An abiotic mechanism involving a free radical intermediate has been proposed. The abstraction of vicinal dihalides (also termed dehalogenation) is another reduction that may have an abiotic component in natural systems. Reductive dehalogenation of aryl halides has recently been reported and further study of this reaction is needed. Several other degradation reactions of organohalides that occur in anaerobic environments are mentioned, the most important of which is dehydrohalogenation. The reduction of nitro groups to amines has also been thoroughly studied. The reactions can occur abiotically, and are affected by the redox conditions of the experimental system. However, a relationship between nitro-reduction rate and measured redox potential has not been clearly established. Reductive dealkylation of the N- and O-heteroatom of hydrocarbon pollutants has been observed but not investigated in detail. Azo compounds can be reduced to their hydrazo derivatives and a thorough study of this reaction indicates that it can be caused by extracellular electron transfer agents. Quinone-hydroquinone couples are important reactive groups in humic materials and similar structures in resazurin and indigo carmine make them useful as models for environmental redox conditions. The interconversion of sulfones, sulfoxides, and sulfides is a redox process and is implicated in the degradation of several pesticides though the reactions need more study. Two reductive heterocyclic cleavage reactions are also mentioned. Finally, several

  3. Protein Synthesis Inhibition Activity by Strawberry Tissue Protein Extracts during Plant Life Cycle and under Biotic and Abiotic Stresses

    Directory of Open Access Journals (Sweden)

    Walther Faedi

    2013-07-01

    Full Text Available Ribosome-inactivating proteins (RIPs, enzymes that are widely distributed in the plant kingdom, inhibit protein synthesis by depurinating rRNA and many other polynucleotidic substrates. Although RIPs show antiviral, antifungal, and insecticidal activities, their biological and physiological roles are not completely understood. Additionally, it has been described that RIP expression is augmented under stressful conditions. In this study, we evaluated protein synthesis inhibition activity in partially purified basic proteins (hereafter referred to as RIP activity from tissue extracts of Fragaria × ananassa (strawberry cultivars with low (Dora and high (Record tolerance to root pathogens and fructification stress. Association between the presence of RIP activity and the crop management (organic or integrated soil, growth stage (quiescence, flowering, and fructification, and exogenous stress (drought were investigated. RIP activity was found in every tissue tested (roots, rhizomes, leaves, buds, flowers, and fruits and under each tested condition. However, significant differences in RIP distribution were observed depending on the soil and growth stage, and an increase in RIP activity was found in the leaves of drought-stressed plants. These results suggest that RIP expression and activity could represent a response mechanism against biotic and abiotic stresses and could be a useful tool in selecting stress-resistant strawberry genotypes.

  4. Abiotic Stress Tolerance: From Gene Discovery in Model Organisms to Crop Improvement

    Institute of Scientific and Technical Information of China (English)

    Ray Bressan; Hans Bohnert; Jian-Kang Zhu

    2009-01-01

    Productive and sustainable agriculture necessitates growing plants in sub-optimal environments with less input of precious resources such as fresh water. For a better understanding and rapid improvement of abiotic stress tolerance, it is important to link physiological and biochemical work to molecular studies in genetically tractable model organisms. With the use of several technologies for the discovery of stress tolerance genes and their appropriate alleles,transgenic approaches to improving stress tolerance in crops remarkably parallels breeding principles with a greatly expanded germplasm base and will succeed eventually.

  5. A novel source of atmospheric H2: abiotic degradation of organic material

    Directory of Open Access Journals (Sweden)

    H. L. Throop

    2012-11-01

    Full Text Available Molecular hydrogen (H2 plays an important role in atmospheric chemistry by competing for reactions with the hydroxyl radical (OH· and contributing to the production of H2O in the stratosphere, indirectly influencing stratospheric ozone concentrations. The dominant pathway for loss of H2 from the atmosphere is via microbially-mediated soil uptake, although the magnitude of this loss is still regarded as highly uncertain. Recent studies have shown that abiotic processes such as photochemically mediated degradation (photodegradation of organic material result in direct emissions of carbon (C and nitrogen (N-based trace gases as well as H2. This H2 production has important implications on source-sink dynamics of H2 at the soil-atmosphere interface and thus it is important to quantify its variability over a range of plant types and materials. Here, we show laboratory observations of H2 production and its temperature dependence during abiotic degradation of four plant litter types as well as pure cellulose and high lignin content woody material. A greater amount of H2 was produced in the absence of solar radiation than from photodegradation alone, verifying that low temperature thermal degradation of plant litter is a source of H2. In addition, we measured a significant release of H2 both in the presence and absence of O2. Our results suggest that abiotic release of H2 during organic matter degradation is ubiquitous in arid ecosystems and may also occur in other terrestrial ecosystems. We propose that because these processes occur at the soil-atmosphere interface, they provide a previously unrecognized proximal source of H2 for microbial uptake and confound interpretation of direct measurements of atmospheric uptake that are important for constraining the global H2 budget.

  6. Induction of Glutathione Synthesis and Glutathione Reductase Activity by Abiotic Stresses in Maize and Wheat

    Directory of Open Access Journals (Sweden)

    Gábor Kocsy

    2002-01-01

    Full Text Available The effect of different abiotic stresses (extreme temperatures and osmotic stress on the synthesis of glutathione and hydroxymethylglutathione, on the ratio of the reduced to oxidised forms of these thiols (GSH/GSSG, hmGSH/hmGSSG, and on the glutathione reductase (GR activity was studied in maize and wheat genotypes having different sensitivity to low temperature stress. Cold treatment induced a greater increase in total glutathione (TG content and in GR activity in tolerant genotypes of both species than in sensitive ones. The GSH/GSSG and hmGSH/hmGSSG ratios were increased by this treatment only in the frost-tolerant wheat variety. High-temperature stress increased the TG content and the GSH/GSSG ratio only in the chilling-sensitive maize genotype, but GR activity was greater after this treatment in both maize genotypes. Osmotic stress resulted in a great increase in the TG content in wheat and the GR activity in maize. The amount of total hydroxymethylglutathione increased following all stress treatments. These results indicate the involvement of these antioxidants in the stress responses of wheat and maize.

  7. Kojic acid in organic synthesis

    OpenAIRE

    ZIRAK, MARYAM; Eftekhari-Sis, Bagher

    2015-01-01

    The reactions of kojic acid in organic synthesis are reviewed. The aim of this review is to cover the literature up to the end of 2014, showing the distribution of publications involving kojic acid chemistry in the synthesis of various pyrone containing compounds, pyridine and pyridone heterocycles, and also other organic compounds. First, introductory text about the preparation, biological, and industrial applications, and the chemical properties of kojic acid is given. Then its uses in orga...

  8. Heterogeneous photocatalysts in organic synthesis

    International Nuclear Information System (INIS)

    The review deals with the application of inorganic semiconductors in organic synthesis. Although the majority of reported reactions still aim at the photocatalytic decomposition of organic compounds, the number of examples in synthetic applications is growing. The principal mechanisms of heterogeneous semiconductor photocatalysis are considered and examples illustrating the use of inorganic semiconductors in organic synthesis are given. The discussion is arranged according to the required excitation wavelength (UV or visible light) and to the new bond that is formed (carbon–carbon or carbon–heteroatom bond). The bibliography includes 47 references

  9. History of Martian volatiles - Implications for organic synthesis.

    Science.gov (United States)

    Fanale, F. P.

    1971-01-01

    A theoretical reconstruction of the history of Martian volatiles indicates that Mars probably possessed a substantial reducing atmosphere at the outset of its history, and that its present tenuous and more oxidized atmosphere is the result of extensive chemical evolution. As a consequence, it is probable that Martian atmospheric chemical conditions, now hostile with respect to abiotic organic synthesis in the gas phase, were initially favorable. Evidence indicating the chronology and degradational history of Martian surface features, surface mineralogy, bulk volatile content, internal mass distribution, and thermal history suggests that Mars catastrophically developed a substantial reducing atmosphere as the result of rapid accretion.

  10. Matrix Embedded Organic Synthesis

    Science.gov (United States)

    Kamakolanu, U. G.; Freund, F. T.

    2016-05-01

    In the matrix of minerals such as olivine, a redox reaction of the low-z elements occurs. Oxygen is oxidized to the peroxy state while the low-Z-elements become chemically reduced. We assign them a formula [CxHyOzNiSj]n- and call them proto-organics.

  11. Abiotic synthesis of acylglycerols under simulated hydrothermal conditions and micelle formation

    Science.gov (United States)

    Simoneit, B.; Rushdi, A.; Deamer, D.

    Abiotic formation of aliphatic lipid compounds i e fatty acids alcohols and acylglycerols has been reported to occur at elevated temperatures and pressures under simulated hydrothermal conditions McCollom et al 1999 Rushdi and Simoneit 2001 2006 Although abiotic chemistry may occur at these conditions the prebiotic self-assembly of micelles to bilayer to vesicles protocells may have occurred elsewhere Amphipathic compounds such as fatty acids and acylglycerols are important candidates for micelle bilayer vesicle formation Thus it is of interest to demonstrate that abiotic lipids amphiphiles precursor compounds for abiotic cellular membranes Deamer 1997 can be synthesized under hydrothermal conditions Hydrothermal experiments were conducted to study condensation reactions of model lipid precursors in aqueous media to form acylglycerols glyceryl alkanoates at elevated temperatures under confining pressures Stainless steel vessels 316SS Sno-Trik high pressure couplings with internal capacities of 286 underline 2 mu l were used for the condensation reactions using a mixture of 0 14 mM glycerol and 0 35 mM of n-alkanoic acid Nine different alkanoic acids ranging from C 7 to C 16 except C 8 were used in these experiments The condensation products were two isomers each of monoacylglycerols and diacylglycerols as well as the corresponding triacylglycerol The product yields were 13-28 for monoacylglycerols 6-13 for diacylglycerols and 1-4 for triacylglycerols The results indicated that 1

  12. Mud, Macrofauna and Microbes: An ode to benthic organism-abiotic interactions at varying scales

    Science.gov (United States)

    Benthic environments are dynamic habitats, subject to variable sources and rates of sediment delivery, reworking from the abiotic and biotic processes, and complex biogeochemistry. These activities do not occur in a vacuum, and interact synergistically to influence food webs, bi...

  13. The energetics of organic synthesis inside and outside the cell.

    Science.gov (United States)

    Amend, Jan P; LaRowe, Douglas E; McCollom, Thomas M; Shock, Everett L

    2013-07-19

    Thermodynamic modelling of organic synthesis has largely been focused on deep-sea hydrothermal systems. When seawater mixes with hydrothermal fluids, redox gradients are established that serve as potential energy sources for the formation of organic compounds and biomolecules from inorganic starting materials. This energetic drive, which varies substantially depending on the type of host rock, is present and available both for abiotic (outside the cell) and biotic (inside the cell) processes. Here, we review and interpret a library of theoretical studies that target organic synthesis energetics. The biogeochemical scenarios evaluated include those in present-day hydrothermal systems and in putative early Earth environments. It is consistently and repeatedly shown in these studies that the formation of relatively simple organic compounds and biomolecules can be energy-yielding (exergonic) at conditions that occur in hydrothermal systems. Expanding on our ability to calculate biomass synthesis energetics, we also present here a new approach for estimating the energetics of polymerization reactions, specifically those associated with polypeptide formation from the requisite amino acids.

  14. The energetics of organic synthesis inside and outside the cell

    Science.gov (United States)

    Amend, Jan P.; LaRowe, Douglas E.; McCollom, Thomas M.; Shock, Everett L.

    2013-01-01

    Thermodynamic modelling of organic synthesis has largely been focused on deep-sea hydrothermal systems. When seawater mixes with hydrothermal fluids, redox gradients are established that serve as potential energy sources for the formation of organic compounds and biomolecules from inorganic starting materials. This energetic drive, which varies substantially depending on the type of host rock, is present and available both for abiotic (outside the cell) and biotic (inside the cell) processes. Here, we review and interpret a library of theoretical studies that target organic synthesis energetics. The biogeochemical scenarios evaluated include those in present-day hydrothermal systems and in putative early Earth environments. It is consistently and repeatedly shown in these studies that the formation of relatively simple organic compounds and biomolecules can be energy-yielding (exergonic) at conditions that occur in hydrothermal systems. Expanding on our ability to calculate biomass synthesis energetics, we also present here a new approach for estimating the energetics of polymerization reactions, specifically those associated with polypeptide formation from the requisite amino acids. PMID:23754809

  15. Nitrogenous gas emissions induced by abiotic nitrite reactions with soil organic matter of a Norway spruce forest

    Science.gov (United States)

    Wei, Jing; Vereecken, Harry; Schloter, Michael; Brüggemann, Nicolas

    2016-04-01

    As an important intermediate of the nitrogen cycle, nitrite is highly reactive to soil organic matter (SOM) in forest soils under acidic conditions. However, there is little knowledge about how much its abiotic reactions with SOM contribute to nitrogen (N) gas emissions of forest soils till now. In this study, we provide data on N gas (N2O, NO, NO2) emissions from abiotic nitrite reactions with different fractions of soil organic matter in spruce forest soil, as well as the mechanisms involved. Soil samples were taken from the Oh layer at the TERENO-Wüstebach catchment, Germany, where Norway spruce (Picea abies) dominates. SOM was fractionated into dissolved organic matter (DOM), fulvic acid (FA), humic acid (HA) and humin (HN) according to their solubility. The dynamics of simultaneous NOx and N2O emissions were analyzed with a dynamic flow-through chamber system, coupled to an infrared laser absorption analyzer for N2O and a chemo-luminescence analyzer for NOx (NO and NO2), which allowed emission measurements with high time resolution. The 15N labelling technique was used for tracing the fate of nitrite-N towards establishment of a total N balance. When nitrite was added to the soil fractions, a large amount of NOx was immediately emitted, mostly in the form of NO. N2O emission was delayed by approximately 0.5-1 h. The NO and N2O emission pattern could be almost perfectly fitted with the Hill equation. The N2O formation rates increased significantly in the following order: DOM, FA, HA and HN, while the total amounts of the gases emitted increased significantly in the opposite order. These results revealed that abiotic reactions of nitrite with SOM in spruce forest soil play an important role in N gas emissions, while the chemical nature of the different SOM fractions determines the rate and amount of N gas emissions.

  16. Substituted N-Phenylpyrazine-2-carboxamides, Their Synthesis and Evaluation as Herbicides and Abiotic Elicitors

    Directory of Open Access Journals (Sweden)

    Katarína Kráľová

    2007-12-01

    Full Text Available The condensation of substituted pyrazine-2-carboxylic acid chlorides with ring-substituted anilines yielded five substituted pyrazine-2-carboxylic acid amides. Thesynthesis, and analytical, lipophilicity and biological data of the newly synthesizedcompounds are presented in this paper. The photosynthesis inhibition, antialgal activityand the effect of a series of pyrazine derivatives as abiotic elicitors on the accumulation offlavonoids in a callus culture of Ononis arvensis (L. were investigated. The most activeinhibitor of the oxygen evolution rate in spinach chloroplasts was 6-chloro-pyrazine-2-carboxylic acid (3-iodo-4-methylphenyl-amide (2, IC50 = 51.0 μmol·L-1. The highestreduction of chlorophyll content in Chlorella vulgaris was found for 5-tert-butyl-N-(4-chloro-3-methylphenyl-pyrazine-2-carboxamide (3, IC50 = 44.0 μmol·L-1. The maximalflavonoid production (about 900% was reached after a twelve-hour elicitation processwith 6-chloropyrazine-2-carboxylic acid (3-iodo-4-methylphenyl-amide (2.

  17. Fluid Mechanics Optimising Organic Synthesis

    Science.gov (United States)

    Leivadarou, Evgenia; Dalziel, Stuart

    2015-11-01

    The Vortex Fluidic Device (VFD) is a new ``green'' approach in the synthesis of organic chemicals with many industrial applications in biodiesel generation, cosmetics, protein folding and pharmaceutical production. The VFD is a rapidly rotating tube that can operate with a jet feeding drops of liquid reactants to the base of the tube. The aim of this project is to explain the fluid mechanics of the VFD that influence the rate of reactions. The reaction rate is intimately related to the intense shearing that promotes collision between reactant molecules. In the VFD, the highest shears are found at the bottom of the tube in the Rayleigh and the Ekman layer and at the walls in the Stewardson layers. As a step towards optimising the performance of the VFD we present experiments conducted in order to establish the minimum drop volume and maximum rotation rate for maximum axisymmetric spreading without fingering instability. PhD candidate, Department of Applied Mathematics and Theoretical Physics.

  18. Diversity-Oriented Organic Synthesis

    Institute of Scientific and Technical Information of China (English)

    J. Wu

    2005-01-01

    @@ 1Introduction A goal of chemical genetics is to find small molecules that modulate the individual functions of gene products with high potency and high specificity[1,2]. Natural products and natural product-derived compounds provide many of the most striking examples, particularly in terms of their specificity. It seems unlikely that natural products alone will provide the hypothetical "complete" set of small molecules that would allow the functions of all proteins, as well as their individual domains, to be determined. For chemistry to have its maximal effect on biology, efficient methods based on diversity-oriented organic synthesis for discovering this set of small molecules are in great demand(See Fig. 1).

  19. Green chemistry oriented organic synthesis in water.

    Science.gov (United States)

    Simon, Marc-Olivier; Li, Chao-Jun

    2012-02-21

    The use of water as solvent features many benefits such as improving reactivities and selectivities, simplifying the workup procedures, enabling the recycling of the catalyst and allowing mild reaction conditions and protecting-group free synthesis in addition to being benign itself. In addition, exploring organic chemistry in water can lead to uncommon reactivities and selectivities complementing the organic chemists' synthetic toolbox in organic solvents. Studying chemistry in water also allows insight to be gained into Nature's way of chemical synthesis. However, using water as solvent is not always green. This tutorial review briefly discusses organic synthesis in water with a Green Chemistry perspective. PMID:22048162

  20. Green chemistry oriented organic synthesis in water.

    Science.gov (United States)

    Simon, Marc-Olivier; Li, Chao-Jun

    2012-02-21

    The use of water as solvent features many benefits such as improving reactivities and selectivities, simplifying the workup procedures, enabling the recycling of the catalyst and allowing mild reaction conditions and protecting-group free synthesis in addition to being benign itself. In addition, exploring organic chemistry in water can lead to uncommon reactivities and selectivities complementing the organic chemists' synthetic toolbox in organic solvents. Studying chemistry in water also allows insight to be gained into Nature's way of chemical synthesis. However, using water as solvent is not always green. This tutorial review briefly discusses organic synthesis in water with a Green Chemistry perspective.

  1. Rice phospholipase A superfamily: organization, phylogenetic and expression analysis during abiotic stresses and development.

    Directory of Open Access Journals (Sweden)

    Amarjeet Singh

    Full Text Available BACKGROUND: Phospholipase A (PLA is an important group of enzymes responsible for phospholipid hydrolysis in lipid signaling. PLAs have been implicated in abiotic stress signaling and developmental events in various plants species. Genome-wide analysis of PLA superfamily has been carried out in dicot plant Arabidopsis. A comprehensive genome-wide analysis of PLAs has not been presented yet in crop plant rice. METHODOLOGY/PRINCIPAL FINDINGS: A comprehensive bioinformatics analysis identified a total of 31 PLA encoding genes in the rice genome, which are divided into three classes; phospholipase A(1 (PLA(1, patatin like phospholipases (pPLA and low molecular weight secretory phospholipase A(2 (sPLA(2 based on their sequences and phylogeny. A subset of 10 rice PLAs exhibited chromosomal duplication, emphasizing the role of duplication in the expansion of this gene family in rice. Microarray expression profiling revealed a number of PLA members expressing differentially and significantly under abiotic stresses and reproductive development. Comparative expression analysis with Arabidopsis PLAs revealed a high degree of functional conservation between the orthologs in two plant species, which also indicated the vital role of PLAs in stress signaling and plant development across different plant species. Moreover, sub-cellular localization of a few candidates suggests their differential localization and functional role in the lipid signaling. CONCLUSION/SIGNIFICANCE: The comprehensive analysis and expression profiling would provide a critical platform for the functional characterization of the candidate PLA genes in crop plants.

  2. P5CDH affects the pathways contributing to Pro synthesis after ProDH activation by biotic and abiotic stress conditions

    Directory of Open Access Journals (Sweden)

    Yanina Soledad Rizzi

    2015-07-01

    Full Text Available Plants facing adverse conditions usually alter proline (Pro metabolism, generating changes that help restore the cellular homeostasis. These organisms synthesize Pro from glutamate (Glu or ornithine (Orn by two-step reactions that share Δ1 pyrroline-5-carboxylate (P5C as intermediate. In the catabolic process, Pro is converted back to Glu using a different pathway that involves Pro dehydrogenase (ProDH, P5C dehydrogenase (P5CDH, and P5C as intermediate. Little is known about the coordination of the catabolic and biosynthetic routes under stress. To address this issue, we analyzed how P5CDH affects the activation of Pro synthesis, in Arabidopsis tissues that increase ProDH activity by transient exposure to exogenous Pro, or infection with Pseudomonas syringae pv. tomato. Wild type (Col-0 and p5cdh mutant plants subjected to these treatments were used to monitor the Pro, Glu and Orn levels, as well as the expression of genes from Pro metabolism. Col-0 and p5cdh tissues consecutively activated ProDH and Pro biosynthetic genes under both conditions. However, they manifested a different coordination between these routes. When external Pro supply was interrupted, wild type leaves degraded Pro to basal levels at which point Pro synthesis, mainly via Glu, became activated. Under the same condition, p5cdh leaves sustained ProDH induction without reducing the Pro content but rather increasing it, apparently by stimulating the Orn pathway. In response to pathogen infection, both genotypes showed similar trends. While Col-0 plants seemed to induce both Pro biosynthetic routes, p5cdh mutant plants may primarily activate the Orn route. Our study contributes to the functional characterization of P5CDH in biotic and abiotic stress conditions, by revealing its capacity to modulate the fate of P5C, and prevalence of Orn or Glu as Pro precursors in tissues that initially consumed Pro.

  3. An Evaluation of the Critical Parameters for Abiotic Peptide Synthesis in Submarine Hydrothermal Systems

    Science.gov (United States)

    Cleaves, H. J.; Aubrey, A. D.; Bada, J. L.

    2009-04-01

    It has been proposed that oligopeptides may be formed in submarine hydrothermal systems (SHSs). Oligopeptides have been synthesized previously under simulated SHS conditions which are likely geochemically implausible. We have herein investigated the oligomerization of glycine under SHS-like conditions with respect to the limitations imposed by starting amino acid concentration, heating time, and temperature. When 10-1 M glycine solutions were heated at 250°C for diketopiperazine (DKP) were detectable. At 200°C, less oligomerization was noted. Peptides beyond glycylglycine (gly2) and DKP were not detected below 150°C. At 10-2 M initial glycine concentration and below, only gly2, DKP, and gly3 were detected, and then only above 200°C at < 20 min reaction time. Gly3 was undetectable at longer reaction times. The major parameters limiting peptide synthesis in SHSs appear to be concentration, time, and temperature. Given the expected low concentrations of amino acids, the long residence times and range of temperatures in SHSs, it is unlikely that SHS environments were robust sources of even simple peptides. Possible unexplored solutions to the problems presented here are also discussed.

  4. Organic synthesis with stable isotopes

    International Nuclear Information System (INIS)

    Described is a scheme for the synthesis of L-arginine-1-13C utilizing methods developed for the synthesis of L-ornithine-1-13C from L-ornithine-2-13C and then converting ornithine into arginine with the enzyme acylase

  5. Linking the spatial patterns of organisms and abiotic factors to ecosystem function and management: insights from semi-arid environments

    Directory of Open Access Journals (Sweden)

    F. T. Maestre

    2006-12-01

    Full Text Available Numerous theoretical and modeling studies have demonstrated the ecological significance of the spatial patterning of organisms on ecosystem functioning and dynamics. However, there is a paucity of empirical evidence that quantitatively shows how changes in the spatial patterns of the organisms forming biotic communities are directly related to ecosystem structure and functioning. In this article, I review a series of experiments and observational studies conducted in semi-arid environments from Spain (degraded calcareous shrubland, steppes dominated by Stipa tenacissima, and gypsum shrublands to: 1 evaluate whether the spatial patterns of the dominant biotic elements in the community are linked to ecosystem structure and functioning, and 2 test if these patterns, and those of abiotic factors, can be used to improve ecosystem restoration. In the semiarid steppes we found a significant positive relationship between the spatial pattern of the perennial plant community and: i the water status of S. tenacissima and ii perennial species richness and diversity. Experimental plantings conducted in these steppes showed that S. tenacissima facilitated the establishment of shrub seedlings, albeit the magnitude and direction of this effect was dependent on rainfall conditions during the first yr after planting. In the gypsum shrubland, a significant, direct relationship between the spatial pattern of the biological soil crusts and surrogates of ecosystem functioning (soil bulk density and respiration was found. In a degraded shrubland with very low vegetation cover, the survival of an introduced population of the shrub Pistacia lentiscus showed marked spatial patterns, which were related to the spatial patterns of soil properties such as soil compaction and sand content. These results provide empirical evidence on the importance of spatial patterns for maintaining ecosystem structure and functioning in semi-arid ecosystems

  6. Synthesis Road Map Problems in Organic Chemistry

    Science.gov (United States)

    Schaller, Chris P.; Graham, Kate J.; Jones, T. Nicholas

    2014-01-01

    Road map problems ask students to integrate their knowledge of organic reactions with pattern recognition skills to "fill in the blanks" in the synthesis of an organic compound. Students are asked to identify familiar organic reactions in unfamiliar contexts. A practical context, such as a medicinally useful target compound, helps…

  7. Microchannel systems for fine organic synthesis

    Science.gov (United States)

    Makarshin, L. L.; Pai, Z. P.; Parmon, V. N.

    2016-02-01

    Characteristic features of application of microchannel systems in organic synthesis are analyzed. The advantages of such systems over conventional chemical engineering equipment, especially for small-scale processes that require fast implementation in industry to obtain small quantities of the product, are shown. Particular examples of successful use of microchannel reactors for various types of organic synthesis are given, primary attention being devoted to the design features of microchannel reactors. The bibliography includes 118 references.

  8. Tuning the Protein Corona of Hydrogel Nanoparticles: The Synthesis of Abiotic Protein and Peptide Affinity Reagents.

    Science.gov (United States)

    O'Brien, Jeffrey; Shea, Kenneth J

    2016-06-21

    Nanomaterials, when introduced into a complex, protein-rich environment, rapidly acquire a protein corona. The type and amount of proteins that constitute the corona depend significantly on the synthetic identity of the nanomaterial. For example, hydrogel nanoparticles (NPs) such as poly(N-isopropylacrylamide) (NIPAm) have little affinity for plasma proteins; in contrast, carboxylated poly(styrene) NPs acquire a dense protein corona. This range of protein adsorption suggests that the protein corona might be "tuned" by controlling the chemical composition of the NP. In this Account, we demonstrate that small libraries of synthetic polymer NPs incorporating a diverse pool of functional monomers can be screened for candidates with high affinity and selectivity to targeted biomacromolecules. Through directed synthetic evolution of NP compositions, one can tailor the protein corona to create synthetic organic hydrogel polymer NPs with high affinity and specificity to peptide toxins, enzymes, and other functional proteins, as well as to specific domains of large proteins. In addition, many NIPAm NPs undergo a change in morphology as a function of temperature. This transformation often correlates with a significant change in NP-biomacromolecule affinity, resulting in a temperature-dependent protein corona. This temperature dependence has been used to develop NP hydrogels with autonomous affinity switching for the protection of proteins from thermal stress and as a method of biomacromolecule purification through a selective thermally induced catch and release. In addition to temperature, changes in pH or buffer can also alter a NP protein corona composition, a property that has been exploited for protein purification. Finally, synthetic polymer nanoparticles with low nanomolar affinity for a peptide toxin were shown to capture and neutralize the toxin in the bloodstream of living mice. While the development of synthetic polymer alternatives to protein affinity reagents is

  9. Tuning the Protein Corona of Hydrogel Nanoparticles: The Synthesis of Abiotic Protein and Peptide Affinity Reagents.

    Science.gov (United States)

    O'Brien, Jeffrey; Shea, Kenneth J

    2016-06-21

    Nanomaterials, when introduced into a complex, protein-rich environment, rapidly acquire a protein corona. The type and amount of proteins that constitute the corona depend significantly on the synthetic identity of the nanomaterial. For example, hydrogel nanoparticles (NPs) such as poly(N-isopropylacrylamide) (NIPAm) have little affinity for plasma proteins; in contrast, carboxylated poly(styrene) NPs acquire a dense protein corona. This range of protein adsorption suggests that the protein corona might be "tuned" by controlling the chemical composition of the NP. In this Account, we demonstrate that small libraries of synthetic polymer NPs incorporating a diverse pool of functional monomers can be screened for candidates with high affinity and selectivity to targeted biomacromolecules. Through directed synthetic evolution of NP compositions, one can tailor the protein corona to create synthetic organic hydrogel polymer NPs with high affinity and specificity to peptide toxins, enzymes, and other functional proteins, as well as to specific domains of large proteins. In addition, many NIPAm NPs undergo a change in morphology as a function of temperature. This transformation often correlates with a significant change in NP-biomacromolecule affinity, resulting in a temperature-dependent protein corona. This temperature dependence has been used to develop NP hydrogels with autonomous affinity switching for the protection of proteins from thermal stress and as a method of biomacromolecule purification through a selective thermally induced catch and release. In addition to temperature, changes in pH or buffer can also alter a NP protein corona composition, a property that has been exploited for protein purification. Finally, synthetic polymer nanoparticles with low nanomolar affinity for a peptide toxin were shown to capture and neutralize the toxin in the bloodstream of living mice. While the development of synthetic polymer alternatives to protein affinity reagents is

  10. The Solvent Selection framework: solvents for organic synthesis, separation processes and ionic-organic synthesis

    DEFF Research Database (Denmark)

    Mitrofanov, Igor; Sansonetti, Sascha; Abildskov, Jens;

    2012-01-01

    problems are presented: 1) solvent selection and design for organic synthesis, 2) solvent screening and design of solvent mixtures for pharmaceutical applications and 3) ionic liquids selection and design as solvents. The application of the framework is highlighted successfully through case studies...... focusing on solvent replacement problem in organic synthesis and solvent mixture design for ibuprofen respectively....

  11. Sulfur monochloride in organic synthesis

    International Nuclear Information System (INIS)

    The data on the reactivity of sulfur monochloride published in the past 15 years have been reviewed and systematized. The review focuses on the synthesis of acyclic and heterocyclic compounds with the use of S2Cl2. The bibliography includes 154 references

  12. Abiotic and prebiotic phosphorus chemistry

    OpenAIRE

    Micheletti, Gabriele

    2011-01-01

    The chief obstacle to understand the metabolic origin of life or RNA-based life is to identify a plausible mechanism for overcoming the clutter wrought by abiotic chemistry. Probably trough simple abiotic and then prebiotic reactions we could arrive to simple pre-RNA molecules. Here we report a possible preibiotic synthesis for heterocyclic compounds, and a self-assembling process of adenosine phosphates a constituent of RNA. In these processes we use a simple and prebiotic phosphorus cyc...

  13. Reduction of ferrihydrite with adsorbed and coprecipitated organic matter: microbial reduction by Geobacter bremensis vs. abiotic reduction by Na-dithionite

    Science.gov (United States)

    Eusterhues, K.; Hädrich, A.; Neidhardt, J.; Küsel, K.; Keller, T. F.; Jandt, K. D.; Totsche, K. U.

    2014-09-01

    Ferrihydrite is a widespread poorly crystalline Fe oxide which becomes easily coated by natural organic matter in the environment. This mineral-bound organic matter entirely changes the mineral surface properties and therefore the reactivity of the original mineral. Here, we investigated 2-line ferrihydrite, ferrihydrite with adsorbed organic matter, and ferrihydrite coprecipitated with organic matter for microbial and abiotic reduction of Fe(III). Ferrihydrite-organic matter associations with different organic matter loadings were reduced either by Geobacter bremensis or abiotically by Na-dithionite. Both types of experiments showed decreasing initial Fe-reduction rates and decreasing degrees of reduction with increasing amounts of mineral-bound organic matter. At similar organic matter loadings, coprecipitated ferrihydrites were more reactive than ferrihydrites with adsorbed organic matter. The difference can be explained by the smaller crystal size and poor crystallinity of such coprecipitates. At small organic matter loadings the poor crystallinity of coprecipitates led to even faster Fe-reduction rates than found for pure ferrihydrite. The amount of mineral-bound organic matter also affected the formation of secondary minerals: goethite was only found after reduction of organic matter-free ferrihydrite and siderite was only detected when ferrihydrites with relatively low amounts of mineral-bound organic matter were reduced. We conclude that direct contact of G. bremensis to the Fe oxide mineral surface was inhibited by attached organic matter. Consequently, mineral-bound organic matter shall be taken into account as a factor in slowing down reductive dissolution.

  14. Molecular evidence for abiotic sulfurization of dissolved organic matter in marine shallow hydrothermal systems

    Science.gov (United States)

    Gomez-Saez, Gonzalo V.; Niggemann, Jutta; Dittmar, Thorsten; Pohlabeln, Anika M.; Lang, Susan Q.; Noowong, Ann; Pichler, Thomas; Wörmer, Lars; Bühring, Solveig I.

    2016-10-01

    Shallow submarine hydrothermal systems are extreme environments with strong redox gradients at the interface of hot, reduced fluids and cold, oxygenated seawater. Hydrothermal fluids are often depleted in sulfate when compared to surrounding seawater and can contain high concentrations of hydrogen sulfide (H2S). It is well known that sulfur in its various oxidation states plays an important role in processing and transformation of organic matter. However, the formation and the reactivity of dissolved organic sulfur (DOS) in the water column at hydrothermal systems are so far not well understood. We investigated DOS dynamics and its relation to the physicochemical environment by studying the molecular composition of dissolved organic matter (DOM) in three contrasting shallow hydrothermal systems off Milos (Eastern Mediterranean), Dominica (Caribbean Sea) and Iceland (North Atlantic). We used ultra-high resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) to characterize the DOM on a molecular level. The molecular information was complemented with general geochemical data, quantitative dissolved organic carbon (DOC) and DOS analyses as well as isotopic measurements (δ2H, δ18O and F14C). In contrast to the predominantly meteoric fluids from Dominica and Iceland, hydrothermal fluids from Milos were mainly fed by recirculating seawater. The hydrothermal fluids from Milos were enriched in H2S and DOS, as indicated by high DOS/DOC ratios and by the fact that >90% of all assigned DOM formulas that were exclusively present in the fluids contained sulfur. In all three systems, DOS from hydrothermal fluids had on average lower O/C ratios (0.26-0.34) than surrounding surface seawater DOS (0.45-0.52), suggesting shallow hydrothermal systems as a source of reduced DOS, which will likely get oxidized upon contact with oxygenated seawater. Evaluation of hypothetical sulfurization reactions suggests DOM reduction and sulfurization during seawater

  15. Coupling effects of abiotic and biotic factors on molecular composition of dissolved organic matter in a freshwater wetland.

    Science.gov (United States)

    He, Wei; Choi, Ilhwan; Lee, Jung-Joon; Hur, Jin

    2016-02-15

    In this study, temporal and spatial variations in five defined molecular size fractions of dissolved organic matter (DOM) were examined for a well preserved wetland (Upo Wetland) and its surrounding areas, and the influencing factors were explored with many biotic and abioic parameters. For each DOM sample, the five size fractions were determined by size-exclusion chromatography coupled with organic carbon detector (SEC-OCD). For 2-year long monthly monitoring, bio-polymers (BP), humic substances (HS), building blocks (BB), low molecular-weight (LMW) neutrals, and LMW acids displayed the median values of 264, 1884, 1070, 1090, and 11 μg-CL(-1), respectively, accounting for 6.2%, 41.7%, 24.5%, 26.4%, and 0.4% of dissolved organic carbon (DOC). The dominant presence of HS indicated that terrestrial input played important roles in DOM composition of the freshwater ecosystem, which contrasted with coastal wetlands in other reports. Both seasonal and periodic patterns in the variations were found only for HS and BB among the size fractions. It was also notable that the sources of HS were seasonally shifted from aquagenic origin in winter to pedogenic origin in summer. The correlations among the size fractions revealed that BB and LMW neutrals might be degradation products from HS and humic-like substances (HS+BB), respectively, while LMW acids, from LMW neutrals. Principle component analysis revealed that the humic-like substances and the aromaticity of DOM were associated with temperature, chlorophyll a, phosphorous, and rainfall, whereas the other fractions and the molecular weight of HS were primarily affected by solar irradiation. Significant correlations between DOM composition and some biotic factors further suggested that DOM may even affect the biological communities, which provides an insight into the potential coupling effects of biotic and abiotic factors on DOM molecular composition in freshwater wetlands.

  16. Coupling effects of abiotic and biotic factors on molecular composition of dissolved organic matter in a freshwater wetland.

    Science.gov (United States)

    He, Wei; Choi, Ilhwan; Lee, Jung-Joon; Hur, Jin

    2016-02-15

    In this study, temporal and spatial variations in five defined molecular size fractions of dissolved organic matter (DOM) were examined for a well preserved wetland (Upo Wetland) and its surrounding areas, and the influencing factors were explored with many biotic and abioic parameters. For each DOM sample, the five size fractions were determined by size-exclusion chromatography coupled with organic carbon detector (SEC-OCD). For 2-year long monthly monitoring, bio-polymers (BP), humic substances (HS), building blocks (BB), low molecular-weight (LMW) neutrals, and LMW acids displayed the median values of 264, 1884, 1070, 1090, and 11 μg-CL(-1), respectively, accounting for 6.2%, 41.7%, 24.5%, 26.4%, and 0.4% of dissolved organic carbon (DOC). The dominant presence of HS indicated that terrestrial input played important roles in DOM composition of the freshwater ecosystem, which contrasted with coastal wetlands in other reports. Both seasonal and periodic patterns in the variations were found only for HS and BB among the size fractions. It was also notable that the sources of HS were seasonally shifted from aquagenic origin in winter to pedogenic origin in summer. The correlations among the size fractions revealed that BB and LMW neutrals might be degradation products from HS and humic-like substances (HS+BB), respectively, while LMW acids, from LMW neutrals. Principle component analysis revealed that the humic-like substances and the aromaticity of DOM were associated with temperature, chlorophyll a, phosphorous, and rainfall, whereas the other fractions and the molecular weight of HS were primarily affected by solar irradiation. Significant correlations between DOM composition and some biotic factors further suggested that DOM may even affect the biological communities, which provides an insight into the potential coupling effects of biotic and abiotic factors on DOM molecular composition in freshwater wetlands. PMID:26674681

  17. Pyrolysis-GCMS Analysis of Solid Organic Products from Catalytic Fischer-Tropsch Synthesis Experiments

    Science.gov (United States)

    Locke, Darren R.; Yazzie, Cyriah A.; Burton, Aaron S.; Niles, Paul B.; Johnson, Natasha M.

    2015-01-01

    Abiotic synthesis of complex organic compounds in the early solar nebula that formed our solar system is hypothesized to occur via a Fischer-Tropsch type (FTT) synthesis involving the reaction of hydrogen and carbon monoxide gases over metal and metal oxide catalysts. In general, at low temperatures (less than 200 C), FTT synthesis is expected to form abundant alkane compounds while at higher temperatures (greater than 200 C) it is expected to product lesser amounts of n-alkanes and greater amounts of alkene, alcohol, and polycyclic aromatic hydrocarbons (PAHs). Experiments utilizing a closed-gas circulation system to study the effects of FTT reaction temperature, catalysts, and number of experimental cycles on the resulting solid insoluble organic products are being performed in the laboratory at NASA Goddard Space Flight Center. These experiments aim to determine whether or not FTT reactions on grain surfaces in the protosolar nebula could be the source of the insoluble organic matter observed in meteorites. The resulting solid organic products are being analyzed at NASA Johnson Space Center by pyrolysis gas chromatography mass spectrometry (PY-GCMS). PY-GCMS yields the types and distribution of organic compounds released from the insoluble organic matter generated from the FTT reactions. Previously, exploratory work utilizing PY-GCMS to characterize the deposited organic materials from these reactions has been reported. Presented here are new organic analyses using magnetite catalyst to produce solid insoluble organic FTT products with varying reaction temperatures and number of experimental cycles.

  18. Carbon Isotope Systematics in Mineral-Catalyzed Hydrothermal Organic Synthesis Processes at High Temperature and Pressures

    Science.gov (United States)

    Fu, Qi; Socki, R. A.; Niles, Paul B.

    2011-01-01

    Observation of methane in the Martian atmosphere has been reported by different detection techniques. Reduction of CO2 and/or CO during serpentization by mineral surface catalyzed Fischer-Tropsch Type (FTT) synthesis may be one possible process responsible for methane generation on Mars. With the evidence a recent study has discovered for serpentinization in deeply buried carbon rich sediments, and more showing extensive water-rock interaction in Martian history, it seems likely that abiotic methane generation via serpentinization reactions may have been common on Mars. Experiments involving mineral-catalyzed hydrothermal organic synthesis processes were conducted at 750 C and 5.5 Kbars. Alkanes, alcohols and carboxylic acids were identified as organic compounds. No "isotopic reversal" of delta C-13 values was observed for alkanes or carboxylic acids, suggesting a different reaction pathway than polymerization. Alcohols were proposed as intermediaries formed on mineral surfaces at experimental conditions. Carbon isotope data were used in this study to unravel the reaction pathways of abiotic formation of organic compounds in hydrothermal systems at high temperatures and pressures. They are instrumental in constraining the origin and evolution history of organic compounds on Mars and other planets.

  19. Magnetically retrievable catalysts for organic synthesis

    Science.gov (United States)

    The use of magnetic nanoparticles (MNPs) as a catalyst in organic synthesis has become a subject of intense investigation. The recovery of expensive catalysts after catalytic reaction and reusing it without losing its activity is an important feature in the sustainable process de...

  20. Asymmetric catalysis in organic synthesis

    Energy Technology Data Exchange (ETDEWEB)

    Reilly, S.D.; Click, D.R.; Grumbine, S.K.; Scott, B.L.; Watkins, J.G.

    1998-11-01

    This is the final report of a three-year, Laboratory Directed Research and Development (LDRD) project at the Los Alamos National Laboratory (LANL). The goal of the project was to prepare new catalyst systems, which would perform chemical reactions in an enantioselective manner so as to produce only one of the possible optical isomers of the product molecule. The authors have investigated the use of lanthanide metals bearing both diolate and Schiff-base ligands as catalysts for the enantioselective reduction of prochiral ketones to secondary alcohols. The ligands were prepared from cheap, readily available starting materials, and their synthesis was performed in a ''modular'' manner such that tailoring of specific groups within the ligand could be carried out without repeating the entire synthetic procedure. In addition, they have developed a new ligand system for Group IV and lanthanide-based olefin polymerization catalysts. The ligand system is easily prepared from readily available starting materials and offers the opportunity to rapidly prepare a wide range of closely related ligands that differ only in their substitution patterns at an aromatic ring. When attached to a metal center, the ligand system has the potential to carry out polymerization reactions in a stereocontrolled manner.

  1. Abiotic stressors and stress responses

    DEFF Research Database (Denmark)

    Sulmon, Cecile; Van Baaren, Joan; Cabello-Hurtado, Francisco;

    2015-01-01

    Abstract Organisms are regularly subjected to abiotic stressors related to increasing anthropogenic activities, including chemicals and climatic changes that induce major stresses. Based on various key taxa involved in ecosystem functioning (photosynthetic microorganisms, plants, invertebrates), ...

  2. Alkoxyallenes as building blocks for organic synthesis.

    Science.gov (United States)

    Zimmer, Reinhold; Reissig, Hans-Ulrich

    2014-05-01

    Alkoxyallenes are unusually versatile C3 building blocks in organic synthesis. Hence this tutorial review summarizes the most important transformations, including subsequent reactions and their applications in the synthesis of relevant compounds, e.g. natural products. The reactivity patterns involved and the synthons derived from alkoxyallenes are presented. Often alkoxyallenes can serve as substitutes of acrolein or acrolein acetals, utilisation of which has already led to interesting products. Most important is the use of lithiated alkoxyallenes which smoothly react with a variety of electrophiles and lead to products with unique substitution patterns. The heterocycles or carbocycles formed are intermediates for the stereoselective synthesis of natural products or for the preparation of other structurally relevant compounds. The different synthons being put into practice by the use of lithiated alkoxyallenes in these variations will be discussed.

  3. Organic Analysis of Catalytic Fischer-Tropsch Type Synthesis Products: Are they Similar to Organics in Chondritic Meteorites?

    Science.gov (United States)

    Yazzie, Cyriah A.; Locke, Darren R.; Johnson, Natasha M.

    2014-01-01

    Fischer-Tropsch Type (FTT) synthesis of organic compounds has been hypothesized to occur in the early solar nebula that formed our Solar System. FTT is a collection of abiotic chemical reactions that convert a mixture of carbon monoxide and hydrogen over nano-catalysts into hydrocarbons and other more complex aromatic compounds. We hypothesized that FTT can generate similar organic compounds as those seen in chondritic meteorites; fragments of asteroids that are characteristic of the early solar system. Specific goals for this project included: 1) determining the effects of different FTT catalyst, reaction temperature, and cycles on organic compounds produced, 2) imaging of organic coatings found on the catalyst, and 3) comparison of organic compounds produced experimentally by FTT synthesis and those found in the ordinary chondrite LL5 Chelyabinsk meteorite. We used Pyrolysis Gas Chromatography Mass Spectrometry (PY-GCMS) to release organic compounds present in experimental FTT and meteorite samples, and Scanning Electron Microscopy (SEM) to take images of organic films on catalyst grains.

  4. Some Aspects of the Catalytic Organic Synthesis

    Institute of Scientific and Technical Information of China (English)

    Anil; K.Saikia

    2007-01-01

    1 Results Catalytic reactions are gaining importance due to its low cost, operational simplicity, high efficiency and selectivity. It is also getting much attention in green synthesis. Many useful organic reactions, including the acylation of alcohols and aldehydes, carbon-carbon, carbon-nitrogen, carbon-sulfur bond forming and oxidation reactions are carried out by catalyst. We are exploring the catalytic acylation of alcohols and aldehydes in a simple and efficient manner. Catalytic activation of unr...

  5. Catalytic Radical Domino Reactions in Organic Synthesis

    Science.gov (United States)

    Sebren, Leanne J.; Devery, James J.; Stephenson, Corey R.J.

    2014-01-01

    Catalytic radical-based domino reactions represent important advances in synthetic organic chemistry. Their development benefits synthesis by providing atom- and step-economical methods to complex molecules. Intricate combinations of radical, cationic, anionic, oxidative/reductive, and transition metal mechanistic steps result in cyclizations, additions, fragmentations, ring-expansions, and rearrangements. This Perspective summarizes recent developments in the field of catalytic domino processes. PMID:24587964

  6. Biomimetic, Catalytic Oxidation in Organic Synthesis

    Institute of Scientific and Technical Information of China (English)

    Shun-lchi Murahashi

    2005-01-01

    @@ 1Introduction Oxidation is one of the most fundamental reactions in organic synthesis. Owing to the current need to develop forward-looking technology that is environmentally acceptable with respect many aspects. The most attractive approaches are biomimetic oxidation reactions that are closely related to the metabolism of living things. The metabolisms are governed by a variety of enzymes such as cytochrome P-450 and flavoenzyme.Simulation of the function of these enzymes with simple transition metal complex catalyst or organic catalysts led to the discovery of biomimetic, catalytic oxidations with peroxides[1]. We extended such biomimetic methods to the oxidation with molecular oxygen under mild conditions.

  7. EXAFS Investigations of Metal Organic Synthesis Tools

    OpenAIRE

    Ertel, T.; Hörner, W.; Abraham, I; Bertagnolli, H.

    1997-01-01

    Grignard Compounds RMgX (R=organic group ; X=Cl, Br, I) are common tools in inorganic and organic synthesis. The structure of these substances in solution, however, is unknown. To answer this question we performed EXAFS measurements at the Br-K-edge in absorption mode and at the Mg-K-edge in fluorescence mode. From these complementary data a consistent model of the structure of the investigated Grignard compounds in solution is deduced. A similar class of reagents are Reformatsky compounds RZ...

  8. Flow “Fine” Synthesis: High Yielding and Selective Organic Synthesis by Flow Methods

    OpenAIRE

    Kobayashi, Shū

    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 appli...

  9. Organic synthesis in experimental impact shocks

    Science.gov (United States)

    McKay, C. P.; Borucki, W. J.

    1997-01-01

    Laboratory simulations of shocks created with a high-energy laser demonstrate that the efficacy of organic production depends on the molecular, not just the elemental composition of the shocked gas. In a methane-rich mixture that simulates a low-temperature equilibrium mixture of cometary material, hydrogen cyanide and acetylene were produced with yields of 5 x 10(17) molecules per joule. Repeated shocking of the methane-rich mixture produced amine groups, suggesting the possible synthesis of amino acids. No organic molecules were produced in a carbon dioxide-rich mixture, which is at odds with thermodynamic equilibrium approaches to shock chemistry and has implications for the modeling of shock-produced organic molecules on early Earth.

  10. Organic Analysis of Catalytic Fischer-Tropsch Synthesis Products and Ordinary Chondrite Meteorites by Stepwise Pyrolysis-GCMS: Organics in the Early Solar Nebula

    Science.gov (United States)

    Locke, Darren R.; Yazzie, Cyriah A.; Burton, Aaron S.; Niles, Paul B.; Johnson, Natasha M.

    2014-01-01

    Abiotic generation of complex organic compounds, in the early solar nebula that formed our solar system, is hypothesized by some to occur via Fischer-Tropsch (FT) synthesis. In its simplest form, FT synthesis involves the low temperature (synthesis has been utilized in the gas-to-liquid process to convert syngas, produced from coal, natural gas, or biomass, into paraffin waxes that can be cracked to produce liquid diesel fuels. In general, the effect of increasing reaction temperature (>300degC) produces FT products that include lesser amounts of n-alkanes and greater alkene, alcohol, and polycyclic aromatic hydrocarbon (PAH) compounds. We have begun to experimentally investigate FT synthesis in the context of abiotic generation of organic compounds in the early solar nebula. It is generally thought that the early solar nebula included abundant hydrogen and carbon monoxide gases and nano-particulate matter such as iron and metal silicates that could have catalyzed the FT reaction. The effect of FT reaction temperature, catalyst type, and experiment duration on the resulting products is being investigated. These solid organic products are analyzed by thermal-stepwise pyrolysis-GCMS and yield the types and distribution of hydrocarbon compounds released as a function of temperature. We show how the FT products vary by reaction temperature, catalyst type, and experimental duration and compare these products to organic compounds found to be indigenous to ordinary chondrite meteorites. We hypothesize that the origin of organics in some chondritic meteorites, that represent an aggregation of materials from the early solar system, may at least in part be from FT synthesis that occurred in the early solar nebula.

  11. Synthesis-Spectroscopy Roadmap Problems: Discovering Organic Chemistry

    Science.gov (United States)

    Kurth, Laurie L.; Kurth, Mark J.

    2014-01-01

    Organic chemistry problems that interrelate and integrate synthesis with spectroscopy are presented. These synthesis-spectroscopy roadmap (SSR) problems uniquely engage second-year undergraduate organic chemistry students in the personal discovery of organic chemistry. SSR problems counter the memorize-or-bust strategy that many students tend to…

  12. Processes influencing migration of bioavailable organic compounds from polymers - investigated during biotic and abiotic testing under static and non-static conditions with varying S/V-ratios

    DEFF Research Database (Denmark)

    Corfitzen, Charlotte B.; Arvin, Erik; Albrechtsen, Hans-Jørgen

    The migration of bioavailable organic compounds (‘bioavailable migration’) from polymeric materials used for drinking water distribution was investigated by an abiotic test: Extracting materials under sterile conditions, and a biotic test: Extracting materials in presence of bacteria. Both tests....../V-ratios had any effect on the bioavailable migration in the biotic tests. Not to underestimate growth potential of polymers, investigations should thus be performed in the presence of a diverse microbial population with paired measurements of biomass in the water phase and on the material surfaces....

  13. Enantioselective biotransformations of nitriles in organic synthesis.

    Science.gov (United States)

    Wang, Mei-Xiang

    2015-03-17

    The hydration and hydrolysis of nitriles are valuable synthetic methods used to prepare carboxamides and carboxylic acids. However, chemical hydration and hydrolysis of nitriles involve harsh reaction conditions, have low selectivity, and generate large amounts of waste. Therefore, researchers have confined the scope of these reactions to simple nitrile substrates. However, biological transformations of nitriles are highly efficient, chemoselective, and environmentally benign, which has led synthetic organic chemists and biotechologists to study these reactions in detail over the last two decades. In nature, biological systems degrade nitriles via two distinct pathways: nitrilases catalyze the direct hydrolysis of nitriles to afford carboxylic acids with release of ammonia, and nitrile hydratases catalyze the conversion of nitriles into carboxamides, which then furnish carboxylic acids via hydrolysis in the presence of amidases. Researchers have subsequently developed biocatalytic methods into useful industrial processes for the manufacture of commodity chemicals, including acrylamide. Since the late 1990s, research by my group and others has led to enormous progress in the understanding and application of enantioselective biotransformations of nitriles in organic synthesis. In this Account, I summarize the important advances in enantioselective biotransformations of nitriles and amides, with a primary focus on research from my laboratory. I describe microbial whole-cell-catalyzed kinetic resolution of various functionalized nitriles, amino- and hydroxynitriles, and nitriles that contain small rings and the desymmetrization of prochiral and meso dinitriles and diamides. I also demonstrate how we can apply the biocatalytic protocol to synthesize natural products and bioactive compounds. These nitrile biotransformations offer an attractive and unique protocol for the enantioselective synthesis of polyfunctionalized organic compounds that are not readily obtainable by

  14. Novel Aryne Chemistry in Organic Synthesis

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Zhijian [Iowa State Univ., Ames, IA (United States)

    2006-12-12

    Arynes are among the most intensively studied systems in chemistry. However, many aspects of the chemistry of these reactive intermediates are not well understood yet and their use as reagents in synthetic organic chemistry has been somewhat limited, due to the harsh conditions needed to generate arynes and the often uncontrolled reactivity exhibited by these species. Recently, o-silylaryl triflates, which can generate the corresponding arynes under very mild reaction conditions, have been found very useful in organic synthesis. This thesis describes several novel and useful methodologies by employing arynes, which generate from o-silylaryl triflates, in organic synthesis. An efficient, reliable method for the N-arylation of amines, sulfonamides and carbamates, and the O-arylation of phenols and carboxylic acids is described in Chapter 1. Amines, sulfonamides, phenols, and carboxylic acids are good nucleophiles, which can react with arynes generated from a-silylaryl triflates to afford the corresponding N- and O-arylated products in very high yields. The regioselectivity of unsymmetrical arynes has also been studied. A lot of useful, functional groups can tolerate our reaction conditions. Carbazoles and dibenzofurans are important heteroaromatic compounds, which have a variety of biological activities. A variety of substituted carbazoles and dibenzofwans are readily prepared in good to excellent yields starting with the corresponding o-iodoanilines or o-iodophenols and o-silylaryl triflates by a treatment with CsF, followed by a Pd-catalyzed cyclization, which overall provides a one-pot, two-step process. By using this methodology, the carbazole alkaloid mukonine has been concisely synthesized in a very good yield. Insertion of an aryne into a σ-bond between a nucleophile and an electrophile (Nu-E) should potentially be a very beneficial process from the standpoint of organic synthesis. A variety of substituted ketones and sulfoxides have been synthesized in good

  15. Organic Ion Exchangers. Synthesis, Characterization and Applications

    Institute of Scientific and Technical Information of China (English)

    E. S. Dragan

    2005-01-01

    @@ 1Introduction Organic ion exchangers in beads form are the most widely utilized materials in the purification, concentration and separation processes of inorganic and organic ions in many fields of science and industry[1,2]. Some original contributions in the preparation and characterization of porous organic ion exchangers will be summarized first. The main types of synthetic ion exchangers were obtained by polymer-analogous reactions performed on porous styrene-divinylbenzene copolymers (S-DVB)[3,4] and porous acrylonitrile-DVB copolymers (AN-DVB) [5,6]. Porous S-DVB copolymers were used as substrate for the synthesis of weak and strong base anion exchangers by chloromethylation reaction followed by the reaction with secondary or tertiary amines.Different chloromethylation agents were employed. Weak base anion exchangers with tertiary or primary amine groups were prepared starting from AN-DVB copolymers by aminolyse-hydrolyse reaction with asymmetrical diamines or ethylenediamine (EDA), respectively. Strong base anion exchangers were obtained by quaternization reaction with alkyl halides of the tertiary amine groups. Chelating ion exchangers with iminodiacetic groups were prepared by the carboxymethylation reaction of the primary amine groups above mentioned and of those contained in a vinylamine-ethylacrylate-DVB copolymer, vinylamine units being generated by a Hofmann degradation reaction of the primary amide groups contained in the acrylamide-ethylacrylate-DVB copolymerp[7]. An amphoteric ion exchanger was prepared by the hydrolysis of the ester groups after the Hofmann degradation.

  16. Flow "Fine" Synthesis: High Yielding and Selective Organic Synthesis by Flow Methods.

    Science.gov (United States)

    Kobayashi, Shū

    2016-02-18

    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.

  17. Flow "Fine" Synthesis: High Yielding and Selective Organic Synthesis by Flow Methods.

    Science.gov (United States)

    Kobayashi, Shū

    2016-02-18

    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

  18. Multistep organic synthesis of modular photosystems

    Science.gov (United States)

    2012-01-01

    Summary Quite extensive synthetic achievements vanish in the online supporting information of publications on functional systems. Underappreciated, their value is recognized by experts only. As an example, we here focus in on the recent synthesis of multicomponent photosystems with antiparallel charge-transfer cascades in co-axial hole- and electron-transporting channels. The synthetic steps are described one-by-one, starting with commercial starting materials and moving on to key intermediates, such as asparagusic acid, an intriguing natural product, as well as diphosphonate “feet”, and panchromatic naphthalenediimides (NDIs), to finally reach the target molecules. These products are initiators and propagators for self-organizing surface-initiated polymerization (SOSIP), a new method introduced to secure facile access to complex architectures. Chemoorthogonal to the ring-opening disulfide exchange used for SOSIP, hydrazone exchange is then introduced to achieve stack exchange, which is a “switching” technology invented to drill giant holes into SOSIP architectures and fill them with functional π-stacks of free choice. PMID:23015840

  19. Patterns in Organometallic Chemistry with Application in Organic Synthesis.

    Science.gov (United States)

    Schwartz, Jeffrey; Labinger, Jay A.

    1980-01-01

    Of interest in this discussion of organometallic complexes are stoichiometric or catalytic reagents for organic synthesis in the complex transformations observed during synthesis for transition metal organometallic complexes. Detailed are general reaction types from which the chemistry or many transition metal organometallic complexes can be…

  20. Peptide synthesis in neat organic solvents with novel thermostable proteases

    NARCIS (Netherlands)

    Toplak, Ana; Nuijens, Timo; Quaedflieg, Peter J L M; Wu, Bian; Janssen, Dick B

    2015-01-01

    Biocatalytic peptide synthesis will benefit from enzymes that are active at low water levels in organic solvent compositions that allow good substrate and product solubility. To explore the use of proteases from thermophiles for peptide synthesis under such conditions, putative protease genes of the

  1. Synthesis of fluorinated organic compounds using oxygen difluoride

    Science.gov (United States)

    Toy, M. S.

    1971-01-01

    Oxygen difluoride synthesis is a much simpler, higher-yield procedure than reactions originally followed to synthesize various fluorinated organic compounds. Extreme care is taken in working with oxygen difluoride as its reactions present severe explosion hazard.

  2. Use of Bromine and Bromo-Organic Compounds in Organic Synthesis.

    Science.gov (United States)

    Saikia, Indranirekha; Borah, Arun Jyoti; Phukan, Prodeep

    2016-06-22

    Bromination is one of the most important transformations in organic synthesis and can be carried out using bromine and many other bromo compounds. Use of molecular bromine in organic synthesis is well-known. However, due to the hazardous nature of bromine, enormous growth has been witnessed in the past several decades for the development of solid bromine carriers. This review outlines the use of bromine and different bromo-organic compounds in organic synthesis. The applications of bromine, a total of 107 bromo-organic compounds, 11 other brominating agents, and a few natural bromine sources were incorporated. The scope of these reagents for various organic transformations such as bromination, cohalogenation, oxidation, cyclization, ring-opening reactions, substitution, rearrangement, hydrolysis, catalysis, etc. has been described briefly to highlight important aspects of the bromo-organic compounds in organic synthesis.

  3. Reduction of ferrihydrite with adsorbed and coprecipitated organic matter: microbial reduction by Geobacter bremensis vs. abiotic reduction by Na-dithionite

    Directory of Open Access Journals (Sweden)

    K. Eusterhues

    2014-04-01

    Full Text Available Ferrihydrite (Fh is a widespread poorly crystalline Fe oxide which becomes easily coated by natural organic matter (OM in the environment. This mineral-bound OM entirely changes the mineral surface properties and therefore the reactivity of the original mineral. Here, we investigated the reactivity of 2-line Fh, Fh with adsorbed OM and Fh coprecipitated with OM towards microbial and abiotic reduction of Fe(III. As a surrogate for dissolved soil OM we used a water extract of a Podzol forest floor. Fh-OM associations with different OM-loadings were reduced either by Geobacter bremensis or abiotically by Na-dithionite. Both types of experiments showed decreasing initial Fe reduction rates and decreasing degrees of reduction with increasing amounts of mineral-bound OM. At similar OM-loadings, coprecipitated Fhs were more reactive than Fhs with adsorbed OM. The difference can be explained by the smaller crystal size and poor crystallinity of such coprecipitates. At small OM loadings this led to even faster Fe reduction rates than found for pure Fh. The amount of mineral-bound OM also affected the formation of secondary minerals: goethite was only found after reduction of OM-free Fh and siderite was only detected when Fhs with relatively low amounts of mineral-bound OM were reduced. We conclude that direct contact of G. bremensis to the Fe oxide mineral surface was inhibited when blocked by OM. Consequently, mineral-bound OM shall be taken into account besides Fe(II accumulation as a further widespread mechanism to slow down reductive dissolution.

  4. A biocompatible alkene hydrogenation merges organic synthesis with microbial metabolism.

    Science.gov (United States)

    Sirasani, Gopal; Tong, Liuchuan; Balskus, Emily P

    2014-07-21

    Organic chemists and metabolic engineers use orthogonal technologies to construct essential small molecules such as pharmaceuticals and commodity chemicals. While chemists have leveraged the unique capabilities of biological catalysts for small-molecule production, metabolic engineers have not likewise integrated reactions from organic synthesis with the metabolism of living organisms. Reported herein is a method for alkene hydrogenation which utilizes a palladium catalyst and hydrogen gas generated directly by a living microorganism. This biocompatible transformation, which requires both catalyst and microbe, and can be used on a preparative scale, represents a new strategy for chemical synthesis that combines organic chemistry and metabolic engineering.

  5. BIOMIMETIC STRATEGIES IN ORGANIC SYNTHESIS. TERPENES

    OpenAIRE

    V. Kulcitki

    2012-01-01

    The current paper represents an outline of the selected contributions to the biomimetic procedures and approaches for the synthesis of terpenes with complex structure and diverse functionalisation pattern. These include homologation strategies, cyclisations, rearrangements, as well as biomimetic remote functionalisations.

  6. Singing synthesis and the Vocal Tract Organ

    OpenAIRE

    Howard, David Martin

    2014-01-01

    Vocal synthesis has been the subject of investigation since the late 18th century when von Kempelen produced his mechanical ‘speaking machine’. The advert of electronics has enabled a number of different methods of voice synthesis to be realized in practice. Recently with the advent of 3-D printing and magnetic resonance imaging of human vocal tracts, it has been possible to create synthetic vocal sounds that combine both mechanical (3-D printed tracts) and electronic (synthesized larynx soun...

  7. PR gene families of citrus: their organ specific-biotic and abiotic inducible expression profiles based on ESTs approach

    Directory of Open Access Journals (Sweden)

    Magnólia A. Campos

    2007-01-01

    Full Text Available In silico expression profiles, of the discovered 3,103 citrus ESTs putatively encoding for PR protein families (PR-1 to PR-17, were evaluated using the Brazil citrus genome EST CitEST/database. Hierarchical clustering was displayed to identify similarities in expression patterns among citrus PR-like gene families (PRlgf in 33 selected cDNA libraries. In this way, PRlgf preferentially expressed by organ and citrus species, and library conditions were highlighted. Changes in expression profiles of clusters for each of the 17 PRlgf expressed in organs infected by pathogens or drought-stressed citrus species were displayed for relative suppression or induction gene expression in relation to the counterpart control. Overall, few PRlgf showed expression 2-fold higher in pathogen-infected than in uninfected organs, even though the differential expression profiles displayed have been quite diverse among studied species and organs. Furthermore, an insight into some contigs from four PRlgf pointed out putative members of multigene families. They appear to be evolutionarily conserved within citrus species and/or organ- or stress-specifically expressed. Our results represent a starting point regarding the extent of expression pattern differences underlying PRlgf expression and reveal genes that may prove to be useful in studies regarding biotechnological approaches or citrus resistance markers.

  8. The effect of soil mineral phases on the abiotic degradation of selected organic compounds. Final report, June 31, 1990--December 31, 1994

    Energy Technology Data Exchange (ETDEWEB)

    Sandhu, S.S.

    1994-12-31

    Funds were received from the United States Department of Energy to study the effects of soil mineral phases on the rates of abiotic degradation of tetraphenylborate (TPB) and diphenylboronic acid (DPBA). In addition to kaolinite and montmorillonite clay minerals, the role of goethite, corundum, manganite, and rutile in the degradation of organoborates was also evaluated. The effects of DPBA, argon, molecular dioxygen (O{sub 2}), temperature, and organic matter on the degradation of organoborates were also measured. The results indicated that TPB and DPBA degraded rapidly on the mineral surfaces. The initial products generated from the degradation of TPB were DPBA and biphenyl; however, further degradation resulted in the formation of phenylboric acid and phenol which persisted even after TPB disappeared. The data also showed that the rate of TPB degradation was faster in kaolinite, a 1:1 clay mineral, than in montmorillonite, a double layer mineral. The initial degradation of TPB by corundum was much higher than goethite, manganite and rutile. However, no further degradation by this mineral was observed where as the degradation of TPB continued by goethite and rutile minerals. Over all, the degradation rate of TPB was the highest for goethite as compared to the other metal oxide minerals. The degradation of TPB and DPBA was a redox reaction where metals (Fe, Al, Ti, Mn) acted as Lewis acids. DPBA and argon retarded the TPB degradation where as molecular oxygen organic matter and temperature increased the rate of TPB disappearance.

  9. Hygienic assessment of biotic and abiotic metals intake in children organism in the conditions of technogenically contaminated territories.

    OpenAIRE

    Belitskaya, E. N.; Antonova, O. V.

    2016-01-01

    Total daily load and the contribution of the different ways of the lead entry in children’s organism in industrial and control area were calculated. The study of a complex metal intake in the children's organism with air, water and food has shown that in industrial areas its intake is increased and intake of micronutrients  - copper and zinc is reduced as compared to the control area. This work made it possible to draw a conclusion onjustified evidence that chemical loading of the environment...

  10. Methane Sulphonic Acid is Green Catalyst in Organic Synthesis

    OpenAIRE

    Pramod Kulkarni

    2015-01-01

    Methane sulphonic acid is an alkanesulphonic acid and its chemical formula is CH3SO3H. MSA is a strong acid having pKa= 1.9 and completely ionized in 0.1 M in an aqueous solution and has small affinity to oxidize organic compounds, less corrosive and toxic than other mineral acids. MSA is also biodegradable and not evolve toxic gases. Therefore MSA is considered as green acid. Therefore its use in organic synthesis attracts many chemists to use in organic synthesis. In this review we describe...

  11. New Reactions and Strategies in Highly Selective Organic Synthesis

    Institute of Scientific and Technical Information of China (English)

    2011-01-01

    @@ Organic synthetic chemistry is a core area of chemical The achievements in research.this field have greatly enhanced our life quality worldwide by providing an impressive range of useful man-made substances, materials and drugs.However, practical organic synthesis requires high selectivity, productivity, atom economy, cost efficiency, operational simplicity, environmental friendliness, and low energy consumption.It is of great importance to conduct intensive research in the development of new organic reactions, new methods and strategies, as well as the synthesis of bioactive important molecules.

  12. A Multistep Synthesis for an Advanced Undergraduate Organic Chemistry Laboratory

    Science.gov (United States)

    Chang Ji; Peters, Dennis G.

    2006-01-01

    Multistep syntheses are often important components of the undergraduate organic laboratory experience and a three-step synthesis of 5-(2-sulfhydrylethyl) salicylaldehyde was described. The experiment is useful as a special project for an advanced undergraduate organic chemistry laboratory course and offers opportunities for students to master a…

  13. Synthesis of Ibuprofen in the Introductory Organic Laboratory

    Science.gov (United States)

    Kjonaas, Richard A.; Williams, Peggy E.; Counce, David A.; Crawley, Lindsey R.

    2011-01-01

    A method for the synthesis of ibuprofen in introductory organic chemistry laboratory courses is reported. This experiment requires two 3-h lab sessions. All of the reactions and techniques are a standard part of any introductory organic chemistry course. In the first lab session, students reduce p-isobutylacetophenone to an alcohol and then…

  14. Camera-enabled techniques for organic synthesis

    Directory of Open Access Journals (Sweden)

    Steven V. Ley

    2013-05-01

    Full Text Available A great deal of time is spent within synthetic chemistry laboratories on non-value-adding activities such as sample preparation and work-up operations, and labour intensive activities such as extended periods of continued data collection. Using digital cameras connected to computer vision algorithms, camera-enabled apparatus can perform some of these processes in an automated fashion, allowing skilled chemists to spend their time more productively. In this review we describe recent advances in this field of chemical synthesis and discuss how they will lead to advanced synthesis laboratories of the future.

  15. Camera-enabled techniques for organic synthesis

    Science.gov (United States)

    Ingham, Richard J; O’Brien, Matthew; Browne, Duncan L

    2013-01-01

    Summary A great deal of time is spent within synthetic chemistry laboratories on non-value-adding activities such as sample preparation and work-up operations, and labour intensive activities such as extended periods of continued data collection. Using digital cameras connected to computer vision algorithms, camera-enabled apparatus can perform some of these processes in an automated fashion, allowing skilled chemists to spend their time more productively. In this review we describe recent advances in this field of chemical synthesis and discuss how they will lead to advanced synthesis laboratories of the future. PMID:23766820

  16. PR gene families of citrus: their organ specific-biotic and abiotic inducible expression profiles based on ESTs approach

    OpenAIRE

    Magnólia A. Campos; Daniel D. Rosa; Juliana Érika C. Teixeira; Maria Luisa P.N. Targon; De Souza, Alessandra A.; Paiva, Luciano V.; Dagmar R. Stach-Machado; Machado, Marcos A

    2007-01-01

    In silico expression profiles, of the discovered 3,103 citrus ESTs putatively encoding for PR protein families (PR-1 to PR-17), were evaluated using the Brazil citrus genome EST CitEST/database. Hierarchical clustering was displayed to identify similarities in expression patterns among citrus PR-like gene families (PRlgf) in 33 selected cDNA libraries. In this way, PRlgf preferentially expressed by organ and citrus species, and library conditions were highlighted. Changes in expression profil...

  17. A different approach to enantioselective organic synthesis

    DEFF Research Database (Denmark)

    Lennartson, Anders; Olsson, Susanne; Sundberg, Jonas;

    2009-01-01

    Voilà, optical activity: Both enantiomers of 1-chloroindene have been synthesized in high selectivity from solely achiral starting materials, and without using optically active catalysts (see scheme). These symmetry-breaking syntheses provide a proof-of-concept for a new approach to asymmetric sy...... synthesis. NCS=N-chlorosuccinimide....

  18. BIOMIMETIC STRATEGIES IN ORGANIC SYNTHESIS. TERPENES

    Directory of Open Access Journals (Sweden)

    V. Kulcitki

    2012-12-01

    Full Text Available The current paper represents an outline of the selected contributions to the biomimetic procedures and approaches for the synthesis of terpenes with complex structure and diverse functionalisation pattern. These include homologation strategies, cyclisations, rearrangements, as well as biomimetic remote functionalisations.

  19. Transitioning organic synthesis from organic solvents to water. What's your E Factor?

    Science.gov (United States)

    Lipshutz, Bruce H; Ghorai, Subir

    2014-08-01

    Traditional organic chemistry, and organic synthesis in particular, relies heavily on organic solvents, as most reactions involve organic substrates and catalysts that tend to be water-insoluble. Unfortunately, organic solvents make up most of the organic waste created by the chemical enterprise, whether from academic, industrial, or governmental labs. One alternative to organic solvents follows the lead of Nature: water. To circumvent the solubility issues, newly engineered "designer" surfactants offer an opportunity to efficiently enable many of the commonly used transition metal-catalyzed and related reactions in organic synthesis to be run in water, and usually at ambient temperatures. This review focuses on recent progress in this area, where such amphiphiles spontaneously self-aggregate in water. The resulting micellar arrays serve as nanoreactors, obviating organic solvents as the reaction medium, while maximizing environmental benefits.

  20. Transitioning organic synthesis from organic solvents to water. What's your E Factor?

    Science.gov (United States)

    Lipshutz, Bruce H.; Ghorai, Subir

    2014-01-01

    Traditional organic chemistry, and organic synthesis in particular, relies heavily on organic solvents, as most reactions involve organic substrates and catalysts that tend to be water-insoluble. Unfortunately, organic solvents make up most of the organic waste created by the chemical enterprise, whether from academic, industrial, or governmental labs. One alternative to organic solvents follows the lead of Nature: water. To circumvent the solubility issues, newly engineered “designer” surfactants offer an opportunity to efficiently enable many of the commonly used transition metal-catalyzed and related reactions in organic synthesis to be run in water, and usually at ambient temperatures. This review focuses on recent progress in this area, where such amphiphiles spontaneously self-aggregate in water. The resulting micellar arrays serve as nanoreactors, obviating organic solvents as the reaction medium, while maximizing environmental benefits. PMID:25170307

  1. Peptide synthesis in neat organic solvents with novel thermostable proteases.

    Science.gov (United States)

    Toplak, Ana; Nuijens, Timo; Quaedflieg, Peter J L M; Wu, Bian; Janssen, Dick B

    2015-06-01

    Biocatalytic peptide synthesis will benefit from enzymes that are active at low water levels in organic solvent compositions that allow good substrate and product solubility. To explore the use of proteases from thermophiles for peptide synthesis under such conditions, putative protease genes of the subtilase class were cloned from Thermus aquaticus and Deinococcus geothermalis and expressed in Escherichia coli. The purified enzymes were highly thermostable and catalyzed efficient peptide bond synthesis at 80°C and 60°C in neat acetonitrile with excellent conversion (>90%). The enzymes tolerated high levels of N,N-dimethylformamide (DMF) as a cosolvent (40-50% v/v), which improved substrate solubility and gave good conversion in 5+3 peptide condensation reactions. The results suggest that proteases from thermophiles can be used for peptide synthesis under harsh reaction conditions.

  2. Spiro[2.4]hepta-4,6-dienes: synthesis and application in organic synthesis

    Science.gov (United States)

    Menchikov, L. G.; Nefedov, O. M.

    2016-03-01

    This review integrates and describes systematically the data in the field of spiro[2.4]hepta-4,6-dienes published in the past 15 years. The changes in the development of studies that took place during this period are noted. The methods for the synthesis, the reactivity details and key chemical transformations of spiro[2.4]hepta-4,6-dienes are considered, with the emphasis on applications of these compounds in organic synthesis. The bibliography includes 207 references.

  3. Seed-Mediated Synthesis of Metal-Organic Frameworks.

    Science.gov (United States)

    Xu, Hai-Qun; Wang, Kecheng; Ding, Meili; Feng, Dawei; Jiang, Hai-Long; Zhou, Hong-Cai

    2016-04-27

    The synthesis of phase-pure metal-organic frameworks (MOFs) is of prime importance but remains a significant challenge because of the flexible and diversified coordination modes between metal ions and organic linkers. In this work, we report the synthesis of phase-pure MOFs via a facile seed-mediated approach. For several "accompanying" pairs of Zr-porphyrinic MOFs that are prone to yield mixtures, by fixing all reaction parameters except introducing seed crystals, MOFs in phase-pure forms have been obtained because the stage of MOF nucleation, which generates mixed nuclei, is bypassed. In addition, phase-pure MOF isomers with distinct pore structures have also been prepared through such an approach, revealing its versatility. To the best of our knowledge, this is an initial report on seed-assisted synthesis of phase-pure MOFs.

  4. Synthesis and Characterization of Novel Organic Semiconductors

    Institute of Scientific and Technical Information of China (English)

    Prashant; Sonar; Samarendra; P.Singh; Ananth; Dodabalapur; Alan; Sellinger

    2007-01-01

    1 Results Development of new organic semiconductors for use in low-cost,large-area applications is very important for growth of the organic electronic industry.Existing non-polymer based organic semiconductors can be roughly classified into linear,star-shaped,branched or lamellar molecules on the basis of their shape[1]. Generally hole (p-type) and electron (n-type) transporting semiconductors have been prepared from electron donating and accepting π-systems respectively[2]. These materials can be used ...

  5. Organic nanomaterials: synthesis, characterization, and device applications

    CERN Document Server

    Torres, Tomas

    2013-01-01

    Recent developments in nanoscience and nanotechnology have given rise to a new generation of functional organic nanomaterials with controlled morphology and well-defined properties, which enable a broad range of useful applications. This book explores some of the most important of these organic nanomaterials, describing how they are synthesized and characterized. Moreover, the book explains how researchers have incorporated organic nanomaterials into devices for real-world applications.Featuring contributions from an international team of leading nanoscientists, Organic Nanomaterials is divided into five parts:Part One introduces the fundamentals of nanomaterials and self-assembled nanostructuresPart Two examines carbon nanostructures—from fullerenes to carbon nanotubes to graphene—reporting on properties, theoretical studies, and applicationsPart Three investigates key aspects of some inorganic materials, self-assembled monolayers,...

  6. Synthesis of Bisphenol Z: An Organic Chemistry Experiment

    Science.gov (United States)

    Gregor, Richard W.

    2012-01-01

    A student achievable synthesis of bisphenol Z, 4,4'-(cyclohexane-1,1-diyl)diphenol, from the acid-catalyzed reaction of phenol with cyclohexanone is presented. The experiment exemplifies all the usual pedagogy for the standard topic of electrophilic aromatic substitution present in the undergraduate organic chemistry curriculum, while providing…

  7. Creatine Synthesis: An Undergraduate Organic Chemistry Laboratory Experiment

    Science.gov (United States)

    Smith, Andri L.; Tan, Paula

    2006-01-01

    Students in introductory chemistry classes typically appreciate seeing the connection between course content and the "real world". For this reason, we have developed a synthesis of creatine monohydrate--a popular supplement used in sports requiring short bursts of energy--for introductory organic chemistry laboratory courses. Creatine monohydrate…

  8. Synthesis and Chemistry of Organic Geminal Di- and Triazides.

    Science.gov (United States)

    Häring, Andreas P; Kirsch, Stefan F

    2015-11-06

    This review recapitulates all available literature dealing with the synthesis and reactivity of geminal organic di- and triazides. These compound classes are, to a large extent, unexplored despite their promising chemical properties and their simple preparation. In addition, the chemistry of carbonyl diazide (2) and tetraazidomethane (105) is described in separate sections.

  9. Synthesis and Chemistry of Organic Geminal Di- and Triazides

    Directory of Open Access Journals (Sweden)

    Andreas P. Häring

    2015-11-01

    Full Text Available This review recapitulates all available literature dealing with the synthesis and reactivity of geminal organic di- and triazides. These compound classes are, to a large extent, unexplored despite their promising chemical properties and their simple preparation. In addition, the chemistry of carbonyl diazide (2 and tetraazidomethane (105 is described in separate sections.

  10. ULTRASOUND-ASSISTED ORGANIC SYNTHESIS: ALCOHOL OXIDATION AND OLEFIN EPOXIDATION

    Science.gov (United States)

    Ultrasound-assisted Organic Synthesis: Alcohol Oxidation and Olefin EpoxidationUnnikrishnan R Pillai, Endalkachew Sahle-Demessie , Vasudevan Namboodiri, Quiming Zhao, Juluis EnriquezU.S. EPA , 26 W. Martin Luther King Dr. , Cincinnati, OH 45268 Phone: 513-569-773...

  11. Reactivity of organic compounds in catalytic synthesis

    Energy Technology Data Exchange (ETDEWEB)

    Minachev, Kh.M.; Bragin, O.V.

    1978-01-01

    A comprehensive review of 1976 Soviet research on catalysis delivered to the 1977 annual session of the USSR Academy of Science Council on Catalysis (Baku 6/16-20/77) covers hydrocarbon reactions, including hydrogenation and hydrogenolysis, dehydrogenation, olefin dimerization and disproportionation, and cyclization and dehydrocyclization (e.g., piperylene cyclization and ethylene cyclotrimerization); catalytic and physicochemical properties of zeolites, including cracking, dehydrogenation, and hydroisomerization catalytic syntheses and conversion of heterocyclic and functional hydrocarbon derivatives, including partial and total oxidation (e.g., of o-xylene to phthalic anhydride); syntheses of thiophenes from alkanes and hydrogen sulfide over certain dehydrogenation catalysts; catalytic syntheses involving carbon oxides ( e.g., the development of a new heterogeneous catalyst for hydroformylation of olefins), and of Co-MgO zeolitic catalysts for synthesis of aliphatic hydrocarbons from carbon dioxide and hydrogen, and fabrication of high-viscosity lubricating oils over bifunctional aluminosilicate catalysts.

  12. Organic synthesis with olefin metathesis catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Grubbs, R.H. [California Institute of Technology, Pasadena, CA (United States)

    1995-12-31

    Over the past nine years, early transition metal catalysts for the ring opening metathesis polymerization of cyclic olefins have been developed. These catalysts are simple organometallic complexes containing metal carbon multiple bonds that in most cases polymerize olefins by a living process. These catalysts have been used to prepare a family of near monodispersed and structurally homogeneous polymers. A series of group VII ROMP catalysts that allow a wide range of functionality to be incorporated into the polymer side chains have been prepared. The most important member of this family of complexes are the bisphosphinedihalo-ruthenium carbene complexes. These polymerization catalysts can also be used in the synthesis of fine chemicals by ring closing (RCM) and vinyl coupling reactions. The availability of the group VII catalysts allow metathesis to be carried out on highly functionalized substrates such as polypeptides and in unusual environments such as in aqueous emulsions.

  13. Organic electron donors as powerful single-electron reducing agents in organic synthesis.

    Science.gov (United States)

    Broggi, Julie; Terme, Thierry; Vanelle, Patrice

    2014-01-01

    One-electron reduction is commonly used in organic chemistry for the formation of radicals by the stepwise transfer of one or two electrons from a donor to an organic substrate. Besides metallic reagents, single-electron reducers based on neutral organic molecules have emerged as an attractive novel source of reducing electrons. The past 20 years have seen the blossoming of a particular class of organic reducing agents, the electron-rich olefins, and their application in organic synthesis. This Review gives an overview of the different types of organic donors and their specific characteristics in organic transformations.

  14. Abiotic Stress Generates ROS That Signal Expression of Anionic Glutamate Dehydrogenases to Form Glutamate for Proline Synthesis in Tobacco and Grapevine[W

    Science.gov (United States)

    Skopelitis, Damianos S.; Paranychianakis, Nikolaos V.; Paschalidis, Konstantinos A.; Pliakonis, Eleni D.; Delis, Ioannis D.; Yakoumakis, Dimitris I.; Kouvarakis, Antonios; Papadakis, Anastasia K.; Stephanou, Euripides G.; Roubelakis-Angelakis, Kalliopi A.

    2006-01-01

    Glutamate dehydrogenase (GDH) may be a stress-responsive enzyme, as GDH exhibits considerable thermal stability, and de novo synthesis of the α-GDH subunit is induced by exogenous ammonium and senescence. NaCl treatment induces reactive oxygen species (ROS), intracellular ammonia, expression of tobacco (Nicotiana tabacum cv Xanthi) gdh-NAD;A1 encoding the α-subunit of GDH, increase in immunoreactive α-polypeptide, assembly of the anionic isoenzymes, and in vitro GDH aminating activity in tissues from hypergeous plant organs. In vivo aminating GDH activity was confirmed by gas chromatorgraphy–mass spectrometry monitoring of 15N-Glu, 15N-Gln, and 15N-Pro in the presence of methionine sulfoximine and amino oxyacetic acid, inhibitors of Gln synthetase and transaminases, respectively. Along with upregulation of α-GDH by NaCl, isocitrate dehydrogenase genes, which provide 2-oxoglutarate, are also induced. Treatment with menadione also elicits a severalfold increase in ROS and immunoreactive α-polypeptide and GDH activity. This suggests that ROS participate in the signaling pathway for GDH expression and protease activation, which contribute to intracellular hyperammonia. Ammonium ions also mimic the effects of salinity in induction of gdh-NAD;A1 expression. These results, confirmed in tobacco and grape (Vitis vinifera cv Sultanina) tissues, support the hypothesis that the salinity-generated ROS signal induces α-GDH subunit expression, and the anionic iso-GDHs assimilate ammonia, acting as antistress enzymes in ammonia detoxification and production of Glu for Pro synthesis. PMID:17041150

  15. Magnetically Recoverable Ruthenium Catalysts in Organic Synthesis

    OpenAIRE

    Dong Wang; Didier Astruc

    2014-01-01

    Magnetically recyclable catalysts with magnetic nanoparticles (MNPs) are becoming a major trend towards sustainable catalysts. In this area, recyclable supported ruthenium complexes and ruthenium nanoparticles occupy a key place and present great advantages compared to classic catalysts. In this micro-review, attention is focused on the fabrication of MNP-supported ruthenium catalysts and their catalytic applications in various organic syntheses.

  16. Organic Synthesis in Simulated Interstellar Ice Analogs

    Science.gov (United States)

    Dworkin, Jason P.; Bernstein, Max P.; Sandford, Scott A.; Allamandola, Louis J.; Deamer, David W.; Elsila, Jamie; Zare, Richard N.

    2001-01-01

    Comets and carbonaceous micrometeorites may have been significant sources of organic compounds on the early Earth. Ices on grains in interstellar dense molecular clouds contain a variety of simple molecules as well as aromatic molecules of various sizes. While in these clouds the icy grains are processed by ultraviolet light and cosmic radiation which produces more complex organic molecules. We have run laboratory simulations to identify the types of molecules which could have been generated photolytically in pre-cometary ices. Experiments were conducted by forming various realistic interstellar mixed-molecular ices with and without polycyclic aromatic hydrocarbons (PAHs) at approx. 10 K under high vacuum irradiated with UV light from a hydrogen plasma lamp. The residue that remained after warming to room temperature was analyzed by HPLC, and by laser desorption mass spectrometry. The residue contains several classes of compounds which may be of prebiotic significance.

  17. Synthesis and Characteristics of Organic Bentonite Gel

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    The bentonite was modified using Ca-bentonite as a matrix and octadecyl/ hexadecyl ammoniumsized by dispersing it into the dimethyl benzene-methyl alcohol system fully.The optimum process conditions for organic modification were that the coating agent dosage is 22g/L, reaction time is 90 minutes and the pH value of pulp is 10.X-ray diffraction ( XRD ) analysis indicates that the d (001) value of the modified bentonite is 20.532A.The influence of gel temperature on its viscosity characteristic was studied.By analyzing the transmssion electron microscopy (TEM) images and observing the dispersed gel, the nanometer effect of the organic gel was discussed.

  18. 15 CFR 715.1 - Annual declaration requirements for production by synthesis of unscheduled discrete organic...

    Science.gov (United States)

    2010-01-01

    ... production by synthesis of unscheduled discrete organic chemicals (UDOCs). 715.1 Section 715.1 Commerce and... DISCRETE ORGANIC CHEMICALS (UDOCs) § 715.1 Annual declaration requirements for production by synthesis of unscheduled discrete organic chemicals (UDOCs). (a) Declaration of production by synthesis of UDOCs...

  19. Earthworm Is a Versatile and Sustainable Biocatalyst for Organic Synthesis

    Science.gov (United States)

    Guan, Zhi; Chen, Yan-Li; Yuan, Yi; Song, Jian; Yang, Da-Cheng; Xue, Yang; He, Yan-Hong

    2014-01-01

    A crude extract of earthworms was used as an eco-friendly, environmentally benign, and easily accessible biocatalyst for various organic synthesis including the asymmetric direct aldol and Mannich reactions, Henry and Biginelli reactions, direct three-component aza-Diels-Alder reactions for the synthesis of isoquinuclidines, and domino reactions for the synthesis of coumarins. Most of these reactions have never before seen in nature, and moderate to good enantioselectivities in aldol and Mannich reactions were obtained with this earthworm catalyst. The products can be obtained in preparatively useful yields, and the procedure does not require any additional cofactors or special equipment. This work provides an example of a practical way to use sustainable catalysts from nature. PMID:25148527

  20. Halogen Bonding in Organic Synthesis and Organocatalysis.

    Science.gov (United States)

    Bulfield, David; Huber, Stefan M

    2016-10-01

    Halogen bonding is a noncovalent interaction similar to hydrogen bonding, which is based on electrophilic halogen substituents. Hydrogen-bonding-based organocatalysis is a well-established strategy which has found numerous applications in recent years. In light of this, halogen bonding has recently been introduced as a key interaction for the design of activators or organocatalysts that is complementary to hydrogen bonding. This Concept features a discussion on the history and electronic origin of halogen bonding, summarizes all relevant examples of its application in organocatalysis, and provides an overview on the use of cationic or polyfluorinated halogen-bond donors in halide abstraction reactions or in the activation of neutral organic substrates.

  1. SYNTHESIS OF A NEW ORGANIC AEROGEL

    Institute of Scientific and Technical Information of China (English)

    WU Zhichao; ZHANG Zhicheng; ZHANG Manwei

    1996-01-01

    A new organic aerogel made from (N-hydroxymethyl)-acrylamide (NA) and resorcinol is reported. The acidic solution of NA and resorcinol was irradiated by γ-rays with 1200-1800 Gy dose, then was heated to 60℃ for at least 16hr to form transparent sol-gel.The translucent aerogel can be obtained from the sol-gel with CO2 as supercritical fluid.Synthetic conditions (e.g. acidity of the solution, ratio of NA to resorcinol) are discussed.

  2. The design, synthesis, and characterization of novel electronic organic materials

    Science.gov (United States)

    Walker, Wesley Thomas

    pi-conjugated organic molecules have proven to be valuable tools for organic electronics and engineered materials. The ability to manipulate the structure and energy levels of these materials allows them to be tailored to meet the electronic and physical demands of a variety of devices. One particular interest in this field is low band gap organic polymers, specifically those with band gaps below 1.5 eV; these are typically designed by constructing polymers with alternating donor and acceptor moieties in the conjugated backbone of the molecule. An additional area of interest for pi-conjugated organic molecules has been the search for solution-processable small molecules for use in organic solar cells and organic light emitting diodes. Owing to poor film morphologies resulting from solution casting, small molecules are largely thermally deposited, thus limiting the scope to which they can be utilized in devices. This dissertation will outline the design, synthesis, and characterization of a series of low band gap organic polymers with a design motif of alternating thiophene-cyclopentadienone units, resulting in polymers that are shown to have absorptions throughout the visible spectrum and into the infrared, as well as the synthesis and characterization of two classes of small solution processable conjugated molecules: dinaphthocarbazoles and triphenylfluoranthenes.

  3. Computer-assisted design of organic synthesis

    Science.gov (United States)

    Kaminaka, H.

    1986-01-01

    The computer programs to design synthetic pathways of organic compounds have been utilized throughout the world since the first system was reported by Corey in 1969, and the LHASA was reported in1972 to become the predominant system. Many programs have been reported mainly in the United States and Europe, and groups of corporations, especially chemical companies, have been trying to improve programs and increase the efficiency of research. In Japan, unfortunately, no concrete movement in this area has been seen. Of course, it goes without saying that these kinds of programs are effective for efficient research, but the remarkable aspect is that these can present unexpected data to the researchers to stimulate them to develop new ideas.

  4. Towards waste free organic synthesis using nanostructured hybrid silicas

    Science.gov (United States)

    Ciriminna, Rosaria; Ilharco, Laura M.; Pandarus, Valerica; Fidalgo, Alexandra; Béland, François; Pagliaro, Mario

    2014-05-01

    As catalysis and organic synthesis come together again, the need for stable, selective and truly heterogeneous solid catalysts for clean and efficient synthetic organic chemistry has increased. Hybrid silica glasses obtained by the sol-gel nanochemistry approach can be successfully used for the waste-free synthesis of valued chemicals in various applications. This success derives from the deliberate chemical design of hybrid nanostructures capable of immobilizing and stabilizing organocatalytic species and unstable metal nanoparticles. The highly selective activity along with a broad scope and ease of application of these mesoporous materials to high-throughput reactions opens the route to faster, cleaner and more convenient processes for both small and large scale manufacturing of useful molecules.

  5. Asymmetric organic/metal(oxide) hybrid nanoparticles: synthesis and applications.

    Science.gov (United States)

    He, Jie; Liu, Yijing; Hood, Taylor C; Zhang, Peng; Gong, Jinlong; Nie, Zhihong

    2013-06-21

    Asymmetric particles (APs) with broken centrosymmetry are of great interest, due to the asymmetric surface properties and diverse functionalities. In particular, organic/metal(oxide) APs naturally combine the significantly different and complementary properties of organic and inorganic species, leading to their unique applications in various fields. In this review article, we highlighted recent advances in the synthesis and applications of organic/metal(oxide) APs. This type of APs is grounded on chemical or physical interactions between metal(oxide) NPs and organic small molecular or polymeric ligands. The synthetic methodologies were summarized in three categories, including the selective surface modifications, phase separation of mixed ligands on the surface of metal(oxide) NPs, and direct synthesis of APs. We further discussed the unique applications of organic/metal(oxide) APs in self-assembly, sensors, catalysis, and biomedicine, as a result of the distinctions between asymmetrically distributed organic and inorganic components. Finally, challenges and future directions are discussed in an outlook section.

  6. Cell wall remodeling under abiotic stress

    OpenAIRE

    Tenhaken, Raimund

    2015-01-01

    Plants exposed to abiotic stress respond to unfavorable conditions on multiple levels. One challenge under drought stress is to reduce shoot growth while maintaining root growth, a process requiring differential cell wall synthesis and remodeling. Key players in this process are the formation of reactive oxygen species (ROS) and peroxidases, which initially cross-link phenolic compounds and glycoproteins of the cell walls causing stiffening. The function of ROS shifts after having converted a...

  7. Functionalized Carbosilane Dendritic Species as Soluble Support in Organic Synthesis

    NARCIS (Netherlands)

    Koten, G. van; Hovestad, N.J.; Ford, A.; Jastrzebski, J.T.B.H.

    2000-01-01

    A new methodology, which is compatible with the use of reactive organometallic reagents, has been developed for the use of carbosilane dendrimers as soluble supports in organic synthesis. Hydroxy-functionalized dendritic carbosilanes Si[CH2CH2CH2SiMe2(C6H4CH(R)OH)]4 (G0-OH, R = H or (S)-Me) and Si[C

  8. Abiotic CO2 reduction during geologic carbon sequestration facilitated by Fe(II)-bearing minerals

    Science.gov (United States)

    Nielsen, L. C.; Maher, K.; Bird, D. K.; Brown, G. E.; Thomas, B.; Johnson, N. C.; Rosenbauer, R. J.

    2012-12-01

    Redox reactions involving subsurface minerals and fluids and can lead to the abiotic generation of hydrocarbons from CO2 under certain conditions. Depleted oil reservoirs and saline aquifers targeted for geologic carbon sequestration (GCS) can contain significant quantities of minerals such as ferrous chlorite, which could facilitate the abiotic reduction of carbon dioxide to n-carboxylic acids, hydrocarbons, and amorphous carbon (C0). If such reactions occur, the injection of supercritical CO2 (scCO2) could significantly alter the oxidation state of the reservoir and cause extensive reorganization of the stable mineral assemblage via dissolution and reprecipitation reactions. Naturally occurring iron oxide minerals such as magnetite are known to catalyze CO2 reduction, resulting in the synthesis of organic compounds. Magnetite is thermodynamically stable in Fe(II) chlorite-bearing mineral assemblages typical of some reservoir formations. Thermodynamic calculations demonstrate that GCS reservoirs buffered by the chlorite-kaolinite-carbonate(siderite/magnesite)-quartz assemblage favor the reduction of CO2 to n-carboxylic acids, hydrocarbons, and C0, although the extent of abiotic CO2 reduction may be kinetically limited. To investigate the rates of abiotic CO2 reduction in the presence of magnetite, we performed batch abiotic CO2 reduction experiments using a Dickson-type rocking hydrothermal apparatus at temperatures (373 K) and pressures (100 bar) within the range of conditions relevant to GCS. Blank experiments containing CO2 and H2 were used to rule out the possibility of catalytic activity of the experimental apparatus. Reaction of brine-suspended magnetite nanoparticles with scCO2 at H2 partial pressures typical of reservoir rocks - up to 100 and 0.1 bars respectively - was used to investigate the kinetics of magnetite-catalyzed abiotic CO2 reduction. Later experiments introducing ferrous chlorite (ripidolite) were carried out to determine the potential for

  9. Synthesis of Organic Compounds over Selected Types of Catalysts

    Directory of Open Access Journals (Sweden)

    Omar Mohamed Saad Ismail

    2011-05-01

    Full Text Available This study provides an overview for the utilization of different catalytic material in the synthesis of organic compounds for important reactions such as heck reaction, aldol reaction, Diels- Alder and other reactions. Comparisons between multiple catalysts for the same reaction and justifications for developing new catalyzed materials are discussed. The following topics are introduced in this work; (1 solid base catalysts, (2 clay catalysts, (3 palladium catalysts, and (4 catalysts to produce organic compound from CO2. The features of these catalysts a long with the conjugated reactions and their selectivity are explained in details, also, some alternatives for toxic or polluting catalysts used in industry are suggested.

  10. Magnetite as Possible Template for the Synthesis of Chiral Organics in Carbonaceous Chondrites

    Science.gov (United States)

    Chan, Q. H. S.; Zolensky, M. E.

    2014-01-01

    The main goal of the Japanese Aerospace Ex-ploration Agency (JAXA) Hayabusa-2 mission is to visit and return to Earth samples of a C-type asteroid (162173) 1999 JU3 in order to understand the origin and nature of organic materials in the Solar System. Life on Earth shows preference towards the set of organics with particular spatial arrangements, this 'selectivity' is a crucial criterion for life. With only rare exceptions, life 'determines' to use the left- (L-) form over the right- (D-) form of amino acids, resulting in a L-enantiomeric excess (ee). Recent studies have shown that L-ee is found within the alpha-methyl amino acids in meteorites [1, 2], which are amino acids with rare terrestrial occurrence, and thus point towards a plausible abiotic origin for ee. One of the proposed origins of chiral asymmetry of amino acids in meteorites is their formation with the presence of asymmetric catalysts [3]. The catalytic mineral grains acted as a surface at which nebular gases (CO, H2 and NH3) were allowed to condense and react through Fisher Tropsch type (FTT) syntheses to form the organics observed in meteorites [4]. Magnetite is shown to be an effective catalyst of the synthesis of amino acids that are commonly found in meteorites [5]. It has also taken the form as spiral magnetites (a.k.a. 'plaquettes'), which were found in various carbonaceous chondrites (CCs), including C2s Tagish Lake and Esseibi, CI Orgueil, and CR chondrites [e.g., 6, 7, 8]. In addition, L-ee for amino acids are common in the aqueously altered CCs, as opposed to the unaltered CCs [1]. It seems possible that the synthesis of amino acids with chiral preferences is correlated to the alteration process experienced by the asteroid parent body, and related to the configuration of spiral magnetite catalysts. Since C-type asteroids are considered to be enriched in organic matter, and the spectral data of 1999 JU3 indicates a certain de-gree of aqueous alteration [9], the Hayabusa-2 mission serves as

  11. Síntese orgânica limpa Clean organic synthesis

    Directory of Open Access Journals (Sweden)

    Antonio Manzolillo Sanseverino

    2000-02-01

    Full Text Available An introduction to the fundamental concepts and main aspects of organic clean synthesis is given, and relevant industrial examples which have implemented the philosophy of cleaner synthesis are also presented. Recent trends in organic synthesis which are environmentally friendly are also discussed.

  12. Síntese orgânica limpa Clean organic synthesis

    OpenAIRE

    Antonio Manzolillo Sanseverino

    2000-01-01

    An introduction to the fundamental concepts and main aspects of organic clean synthesis is given, and relevant industrial examples which have implemented the philosophy of cleaner synthesis are also presented. Recent trends in organic synthesis which are environmentally friendly are also discussed.

  13. Engineering and Applications of fungal laccases for organic synthesis

    Directory of Open Access Journals (Sweden)

    Ballesteros Antonio

    2008-11-01

    Full Text Available Abstract Laccases are multi-copper containing oxidases (EC 1.10.3.2, widely distributed in fungi, higher plants and bacteria. Laccase catalyses the oxidation of phenols, polyphenols and anilines by one-electron abstraction, with the concomitant reduction of oxygen to water in a four-electron transfer process. In the presence of small redox mediators, laccase offers a broader repertory of oxidations including non-phenolic substrates. Hence, fungal laccases are considered as ideal green catalysts of great biotechnological impact due to their few requirements (they only require air, and they produce water as the only by-product and their broad substrate specificity, including direct bioelectrocatalysis. Thus, laccases and/or laccase-mediator systems find potential applications in bioremediation, paper pulp bleaching, finishing of textiles, bio-fuel cells and more. Significantly, laccases can be used in organic synthesis, as they can perform exquisite transformations ranging from the oxidation of functional groups to the heteromolecular coupling for production of new antibiotics derivatives, or the catalysis of key steps in the synthesis of complex natural products. In this review, the application of fungal laccases and their engineering by rational design and directed evolution for organic synthesis purposes are discussed.

  14. Synthesis and characterization of organically linked ZnO nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Chory, Christine; Riedel, Ingo; Parisi, Juergen [Energy and Semiconductor Research Laboratory (EHF), University of Oldenburg, Carl-von Ossietzky-Strasse 9-11, 26129 Oldenburg (Germany); Kruska, Carsten; Heimbrodt, Wolfram [Department of Physics and Material Sciences Center, Philipps-University Marburg, Renthof 5, 35032 Marburg (Germany); Feser, Clemens [NEXT ENERGY - EWE Research Centre for Energy Technology e.V., Carl-von Ossietzky-Strasse 15, 26129 Oldenburg (Germany); Beenken, Wichard J.D. [Department of Theoretical Physics I, Ilmenau University of Technology, Weimarer Strasse 25, 98693 Ilmenau (Germany); Hoppe, Harald [Department of Experimental Physics I, Ilmenau University of Technology, Weimarer Strasse 32, 98693 Ilmenau (Germany)

    2012-11-15

    We report on the solution-based synthesis and characterization of three-dimensional networks of ZnO nanoparticles where the formation of structures is achieved by covalently linking the nanocrystals with bifunctional organic ligands. The colloidal synthesis will be presented with application of two ligands that vary in size and binding sites. Furthermore we report on structural characterization of dried powders and thin films by means of X-ray diffraction and electron microscopy in order to examine the regularity of the structures. We also present first investigations of the optical properties and electrical conductance behavior in lateral direction of the differently linked hybrid ZnO networks. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  15. Biomineralization-inspired synthesis of functional organic/inorganic hybrid materials: organic molecular control of self-organization of hybrids.

    Science.gov (United States)

    Arakaki, Atsushi; Shimizu, Katsuhiko; Oda, Mayumi; Sakamoto, Takeshi; Nishimura, Tatsuya; Kato, Takashi

    2015-01-28

    Organisms produce various organic/inorganic hybrid materials, which are called biominerals. They form through the self-organization of organic molecules and inorganic elements under ambient conditions. Biominerals often have highly organized and hierarchical structures from nanometer to macroscopic length scales, resulting in their remarkable physical and chemical properties that cannot be obtained by simple accumulation of their organic and inorganic constituents. These observations motivate us to create novel functional materials exhibiting properties superior to conventional materials--both synthetic and natural. Herein, we introduce recent progress in understanding biomineralization processes at the molecular level and the development of organic/inorganic hybrid materials by these processes. We specifically outline fundamental molecular studies on silica, iron oxide, and calcium carbonate biomineralization and describe material synthesis based on these mechanisms. These approaches allow us to design a variety of advanced hybrid materials with desired morphologies, sizes, compositions, and structures through environmentally friendly synthetic routes using functions of organic molecules.

  16. Photocatalytic Anion Oxidation and Applications in Organic Synthesis.

    Science.gov (United States)

    Hering, Thea; Meyer, Andreas Uwe; König, Burkhard

    2016-08-19

    Ions and radicals of the same kind differ by one electron only. The oxidation of many stable inorganic anions yields their corresponding highly reactive radicals, and visible light excitable photocatalysts can provide the required oxidation potential for this transformation. Air oxygen serves as the terminal oxidant, or cheap sacrificial oxidants are used, providing a very practical approach for generating reactive inorganic radicals for organic synthesis. We discuss in this perspective several recently reported examples: Nitrate radicals are obtained by one-electron photooxidation of nitrate anions and are very reactive toward organic molecules. The photooxidation of sulfinate salts yields the much more stable sulfone radicals, which smoothly add to double bonds. A two-electron oxidation of chloride anions to electrophilic chlorine species reacting with arenes in aromatic substitutions extends the method beyond radical reactions. The chloride anion oxidation proceeds via photocatalytically generated peracidic acid as the oxidation reagent. Although the number of reported examples of photocatalytically generated inorganic radical intermediates for organic synthesis is still small, future extension of the concept to other inorganic ions as radical precursors is a clear perspective.

  17. Mechanism for the abiotic synthesis of uracil via UV-induced oxidation of pyrimidine in pure H2O ices under astrophysical conditions

    International Nuclear Information System (INIS)

    The UV photoirradiation of pyrimidine in pure H2O ices has been explored using second-order Moeller-Plesset perturbation theory and density functional theory methods, and compared with experimental results. Mechanisms studied include those starting with neutral pyrimidine or cationic pyrimidine radicals, and reacting with OH radical. The ab initio calculations reveal that the formation of some key species, including the nucleobase uracil, is energetically favored over others. The presence of one or several water molecules is necessary in order to abstract a proton which leads to the final products. Formation of many of the photoproducts in UV-irradiated H2O:pyrimidine=20:1 ice mixtures was established in a previous experimental study. Among all the products, uracil is predicted by quantum chemical calculations to be the most favored, and has been identified in experimental samples by two independent chromatography techniques. The results of the present study strongly support the scenario in which prebiotic molecules, such as the nucleobase uracil, can be formed under abiotic processes in astrophysically relevant environments, namely in condensed phase on the surface of icy, cold grains before being delivered to the telluric planets, like Earth.

  18. Synthesis and Characterization of Functionalized Metal-organic Frameworks

    Science.gov (United States)

    Karagiaridi, Olga; Bury, Wojciech; Sarjeant, Amy A.; Hupp, Joseph T.; Farha, Omar K.

    2014-01-01

    Metal-organic frameworks have attracted extraordinary amounts of research attention, as they are attractive candidates for numerous industrial and technological applications. Their signature property is their ultrahigh porosity, which however imparts a series of challenges when it comes to both constructing them and working with them. Securing desired MOF chemical and physical functionality by linker/node assembly into a highly porous framework of choice can pose difficulties, as less porous and more thermodynamically stable congeners (e.g., other crystalline polymorphs, catenated analogues) are often preferentially obtained by conventional synthesis methods. Once the desired product is obtained, its characterization often requires specialized techniques that address complications potentially arising from, for example, guest-molecule loss or preferential orientation of microcrystallites. Finally, accessing the large voids inside the MOFs for use in applications that involve gases can be problematic, as frameworks may be subject to collapse during removal of solvent molecules (remnants of solvothermal synthesis). In this paper, we describe synthesis and characterization methods routinely utilized in our lab either to solve or circumvent these issues. The methods include solvent-assisted linker exchange, powder X-ray diffraction in capillaries, and materials activation (cavity evacuation) by supercritical CO2 drying. Finally, we provide a protocol for determining a suitable pressure region for applying the Brunauer-Emmett-Teller analysis to nitrogen isotherms, so as to estimate surface area of MOFs with good accuracy. PMID:25225784

  19. Prebiotic Synthesis of Methionine and Other Sulfur-Containing Organic Compounds on the Primitive Earth: A Contemporary Reassessment Based on an Unpublished 1958 Stanley Miller Experiment

    Science.gov (United States)

    Parker, Eric T.; Cleaves, H. James; Callahan, Michael P.; Dworkin, Jason P.; Glavin, Daniel P.; Lazcano, Antonio

    2010-01-01

    Original extracts from an unpublished 1958 experiment conducted by the late Stanley L. Miller were recently found and analyzed using modern state-of-the-art analytical methods. The extracts were produced by the action of an electric discharge on a mixture of methane (CH4), hydrogen sulfide (H2S), ammonia (NH3), and carbon dioxide (CO2). Racemic methionine was farmed in significant yields, together with other sulfur-bearing organic compounds. The formation of methionine and other compounds from a model prebiotic atmosphere that contained H2S suggests that this type of synthesis is robust under reducing conditions, which may have existed either in the global primitive atmosphere or in localized volcanic environments on the early Earth. The presence of a wide array of sulfur-containing organic compounds produced by the decomposition of methionine and cysteine indicates that in addition to abiotic synthetic processes, degradation of organic compounds on the primordial Earth could have been important in diversifying the inventory of molecules of biochemical significance not readily formed from other abiotic reactions, or derived from extraterrestrial delivery.

  20. Electrical energy sources for organic synthesis on the early earth

    Science.gov (United States)

    Chyba, Christopher; Sagan, Carl

    1991-01-01

    It is pointed out that much of the contemporary origin-of-life research uses the original estimates of Miller and Urey (1959) for terrestrial energy dissipation by lightning and coronal discharges being equal to 2 x 10 to the 19th J/yr and 6 x 10 to the 19th J/yr, respectively. However, data from experiments that provide analogues to naturally-occurring lightning and coronal discharges indicate that lightning energy yields for organic synthesis (nmole/J) are about one order of magnitude higher than the coronal discharge yields. This suggests that, on early earth, organic production by lightning may have dominated that due to coronal emission. New values are recommended for lightning and coronal discharge dissipation rates on the early earth, 1 x 10 to the 18th J/yr and 5 x 10 to the 17th J/yr, respectively.

  1. Metal–organic framework membranes: from synthesis to separation application

    KAUST Repository

    Qiu, Shilun

    2014-06-26

    Metal-organic framework (MOF) materials, which are constructed from metal ions or metal ion clusters and bridging organic linkers, exhibit regular crystalline lattices with relatively well-defined pore structures and interesting properties. As a new class of porous solid materials, MOFs are attractive for a variety of industrial applications including separation membranes-a rapidly developing research area. Many reports have discussed the synthesis and applications of MOFs and MOF thin films, but relatively few have addressed MOF membranes. This critical review provides an overview of the diverse MOF membranes that have been prepared, beginning with a brief introduction to the current techniques for the fabrication of MOF membranes. Gas and liquid separation applications with different MOF membranes are also included (175 references). This journal is © the Partner Organisations 2014.

  2. Synthesis of Two Local Anesthetics from Toluene: An Organic Multistep Synthesis in a Project-Oriented Laboratory Course

    Science.gov (United States)

    Demare, Patricia; Regla, Ignacio

    2012-01-01

    This article describes one of the projects in the advanced undergraduate organic chemistry laboratory course concerning the synthesis of two local anesthetic drugs, prilocaine and benzocaine, with a common three-step sequence starting from toluene. Students undertake, in a several-week independent project, the multistep synthesis of a…

  3. Cobalt catalysis involving π components in organic synthesis.

    Science.gov (United States)

    Gandeepan, Parthasarathy; Cheng, Chien-Hong

    2015-04-21

    Over the last three decades, transition-metal-catalyzed organic transformations have been shown to be extremely important in organic synthesis. However, most of the successful reactions are associated with noble metals, which are generally toxic, expensive, and less abundant. Therefore, we have focused on catalysis using the abundant first-row transition metals, specifically cobalt. In this Account, we demonstrate the potential of cobalt catalysis in organic synthesis as revealed by our research. We have developed many useful catalytic systems using cobalt complexes. Overall, they can be classified into several broad types of reactions, specifically [2 + 2 + 2] and [2 + 2] cycloadditions; enyne reductive coupling; reductive [3 + 2] cycloaddition of alkynes/allenes with enones; reductive coupling of alkyl iodides with alkenes; addition of organoboronic acids to alkynes, alkenes, or aldehydes; carbocyclization of o-iodoaryl ketones/aldehydes with alkynes/electron-deficient alkenes; coupling of thiols with aryl and alkyl halides; enyne coupling; and C-H bond activation. Reactions relying on π components, specifically cycloaddition, reductive coupling, and enyne coupling, mostly afford products with excellent stereo- and regioselectivity and superior atom economy. We believe that these cobalt-catalyzed π-component coupling reactions proceed through five-membered cobaltacyclic intermediates formed by the oxidative cyclometalation of two coordinated π bonds of the substrates to the low-valent cobalt species. The high regio- and stereoselectivity of these reactions are achieved as a result of the electronic and steric effects of the π components. Mostly, electron-withdrawing groups and bulkier groups attached to the π bonds prefer to be placed near the cobalt center of the cobaltacycle. Most of these transformations proceed through low-valent cobalt complexes, which are conveniently generated in situ from air-stable Co(II) salts by Zn- or Mn-mediated reduction

  4. Natural Product Total Synthesis in the Organic Laboratory: Total Synthesis of Caffeic Acid Phenethyl Ester (CAPE), a Potent 5-Lipoxygenase Inhibitor from Honeybee Hives

    Science.gov (United States)

    Touaibia, Mohamed; Guay, Michel

    2011-01-01

    Natural products play a critical role in modern organic synthesis and learning synthetic techniques is an important component of the organic laboratory experience. In addition to traditional one-step organic synthesis laboratories, a multistep natural product synthesis is an interesting experiment to challenge students. The proposed three-step…

  5. Organic synthesis - applications in enzymatic studies, catalysis and surface modification

    DEFF Research Database (Denmark)

    Viart, Helene Marie-France

    applications of (phospho)lipids, while the last chapter differs and deals with the synthesis and initial structural studies of a C3symmetric phosphine oxide. In the first chapter, a series of phospholipids have been synthesised in order to perform a short structure-activity relationship study ofan enzyme......: a C3symmetric phosphine oxide has been synthesised, which we intend to test, after reduction to the phosphin, as a ligand in organometallic catalysed reactions. The ultimate goal is to obtain enantioselectivity, introduced by the organization of aryl substituents around phosphorous in our ligand........ According to our theory, two aspects of the enzyme-substrate interactions are primordialfor an effective hydrolysis to occur: the formation of a constructive Michaelis-Menten complex, and access of water to the hydrolysis site. In order to verify this theory, the synthesised phospholipids were formulated...

  6. Gold-Catalyzed Cyclization Processes: Pivotal Avenues for Organic Synthesis.

    Science.gov (United States)

    Kumar, Amit; Singh, Sukhdev; Sharma, Sunil K; Parmar, Virinder S; Van der Eycken, Erik V

    2016-02-01

    Over the years, gold catalysis has materialized as an incredible synthetic approach among the scientific community. Due to the trivial reaction conditions and great functional compatibility, these progressions are synthetically expedient, because practitioners can implement them to build intricate architectures from readily amassed building blocks with high bond forming indices. The incendiary growth of gold catalysts in organic synthesis has been demonstrated as one of the most prevailing soft Lewis acids for electrophilic activation of carbon-carbon multiple bonds towards a great assortment of nucleophiles. Nowadays, organic chemists consistently employ gold catalysts to carry out a diverse array of organic transformations to build unprecedented molecular architectures. Despite all these achievements and a plethora of reports, many vital challenges remain. In this account, we describe the reactivity of various gold catalysts towards cyclization processes developed over the years. These protocols give access to a wide scope of polyheterocyclic structures, containing different medium-sized ring skeletons. This is interesting, as the quest for highly selective reactions to assemble diversely functionalized products has attracted much attention. We envisage that these newly developed chemo-, regio-, and diastereoselective protocols could provide an expedient route to architecturally cumbersome heterocycles of importance for the pharmaceutical industry.

  7. The effect of soil mineral phases on the abiotic degradation of selected organic compounds. Progress report, June 31, 1990--May 31, 1993

    Energy Technology Data Exchange (ETDEWEB)

    Sandhu, S.S.

    1993-05-31

    Tetraphenylborate (TPB) is used to precipitate radioactive 137Cs from high-level nuclear waste water at the Defense Waste Processing Facility (DWPF) operated by the US DOE at the Savannah River Plant (SRP). The process is part of the procedure for the glassification of high-level nuclear waste in preparation for its long-term geological disposal. The decontaminated waste water contains millimolar quantities of TPB that will be processed into salt concretions. The transporation and use of large amounts of TPB can potentially result in the release of TPB into soil or aquatic environments. Previous study has shown that TPB degrades in soils to initially form diphenylborinic acid (DPBA) and biphenyl. DPBA appears to degrade further into other unidentified compounds which subsequently degrade into inorganic boron. The factors which promote the abiotic degradation of TPB need to be investigated since this chemical is used in the processing of radioactive wastes. TPB and its intermediate product, DPBA, have been reported to be toxic to microorganisms and plants, dependent on soil or water environments for their survival and growth.

  8. Abiotic gas: atypical but not rare

    OpenAIRE

    Etiope, G.; Istituto Nazionale di Geofisica e Vulcanologia, Sezione Roma2, Roma, Italia; Schoell, M.

    2014-01-01

    Abiotic gaseous hydrocarbons comprise a fascinating, but poorly understood, group of Earth fl uids generated by magmatic and gas–water–rock reactions that do not directly involve organic matter. At least nine different inorganic mechanisms, including Fischer-Tropsch type reactions, occur over a wide range of temperatures. Trace amounts (typically parts per million by volume) are formed in volcanic and geothermal fl uids, but considerable amounts of methane, reaching 80–90 vol%,...

  9. From Polymer to Small Organic Molecules: A Tight Relationship between Radical Chemistry and Solid-Phase Organic Synthesis

    OpenAIRE

    Danilo Mirizzi; Maurizio Pulici

    2011-01-01

    Since Gomberg’s discovery of radicals as chemical entities, the interest around them has increased through the years. Nowadays, radical chemistry is used in the synthesis of 75% of all polymers, inevitably establishing a close relationship with Solid-Phase Organic Synthesis. More recently, the interest of organic chemists has shifted towards the application of usual “in-solution” radical chemistry to the solid-phase, ranging from the use of supported reagents for radical reactions, to the dev...

  10. Calcium Carbide: A Unique Reagent for Organic Synthesis and Nanotechnology.

    Science.gov (United States)

    Rodygin, Konstantin S; Werner, Georg; Kucherov, Fedor A; Ananikov, Valentine P

    2016-04-01

    Acetylene, HC≡CH, is one of the primary building blocks in synthetic organic and industrial chemistry. Several highly valuable processes have been developed based on this simplest alkyne and the development of acetylene chemistry has had a paramount impact on chemical science over the last few decades. However, in spite of numerous useful possible reactions, the application of gaseous acetylene in everyday research practice is rather limited. Moreover, the practical implementation of high-pressure acetylene chemistry can be very challenging, owing to the risk of explosion and the requirement for complex equipment; special safety precautions need to be taken to store and handle acetylene under high pressure, which limit its routine use in a standard laboratory setup. Amazingly, recent studies have revealed that calcium carbide, CaC2 , can be used as an easy-to-handle and efficient source of acetylene for in situ chemical transformations. Thus, calcium carbide is a stable and inexpensive acetylene precursor that is available on the ton scale and it can be handled with standard laboratory equipment. The application of calcium carbide in organic synthesis will bring a new dimension to the powerful acetylene chemistry.

  11. Organic synthesis toward small-molecule probes and drugs

    Science.gov (United States)

    Schreiber, Stuart L.

    2011-01-01

    Organic synthesis” is a compound-creating activity often focused on biologically active small molecules. This special issue of PNAS explores innovations and trends in the field that are enabling the synthesis of new types of small-molecule probes and drugs. This perspective article frames the research described in the special issue but also explores how these modern capabilities can both foster a new and more extensive view of basic research in the academy and promote the linkage of life-science research to the discovery of novel types of small-molecule therapeutics [Schreiber SL (2009) Chem Bio Chem 10:26–29]. This new view of basic research aims to bridge the chasm between basic scientific discoveries in life sciences and new drugs that treat the root cause of human disease—recently referred to as the “valley of death” for drug discovery. This perspective article describes new roles that modern organic chemistry will need to play in overcoming this challenge. PMID:21464328

  12. Calcium Carbide: A Unique Reagent for Organic Synthesis and Nanotechnology.

    Science.gov (United States)

    Rodygin, Konstantin S; Werner, Georg; Kucherov, Fedor A; Ananikov, Valentine P

    2016-04-01

    Acetylene, HC≡CH, is one of the primary building blocks in synthetic organic and industrial chemistry. Several highly valuable processes have been developed based on this simplest alkyne and the development of acetylene chemistry has had a paramount impact on chemical science over the last few decades. However, in spite of numerous useful possible reactions, the application of gaseous acetylene in everyday research practice is rather limited. Moreover, the practical implementation of high-pressure acetylene chemistry can be very challenging, owing to the risk of explosion and the requirement for complex equipment; special safety precautions need to be taken to store and handle acetylene under high pressure, which limit its routine use in a standard laboratory setup. Amazingly, recent studies have revealed that calcium carbide, CaC2 , can be used as an easy-to-handle and efficient source of acetylene for in situ chemical transformations. Thus, calcium carbide is a stable and inexpensive acetylene precursor that is available on the ton scale and it can be handled with standard laboratory equipment. The application of calcium carbide in organic synthesis will bring a new dimension to the powerful acetylene chemistry. PMID:26898248

  13. Synthesis of 10-Ethyl Flavin: A Multistep Synthesis Organic Chemistry Laboratory Experiment for Upper-Division Undergraduate Students

    Science.gov (United States)

    Sichula, Vincent A.

    2015-01-01

    A multistep synthesis of 10-ethyl flavin was developed as an organic chemistry laboratory experiment for upper-division undergraduate students. Students synthesize 10-ethyl flavin as a bright yellow solid via a five-step sequence. The experiment introduces students to various hands-on experimental organic synthetic techniques, such as column…

  14. Development of new methods in modern selective organic synthesis: preparation of functionalized molecules with atomic precision

    International Nuclear Information System (INIS)

    The challenges of the modern society and the growing demand of high-technology sectors of industrial production bring about a new phase in the development of organic synthesis. A cutting edge of modern synthetic methods is introduction of functional groups and more complex structural units into organic molecules with unprecedented control over the course of chemical transformation. Analysis of the state-of-the-art achievements in selective organic synthesis indicates the appearance of a new trend — the synthesis of organic molecules, biologically active compounds, pharmaceutical substances and smart materials with absolute selectivity. Most advanced approaches to organic synthesis anticipated in the near future can be defined as 'atomic precision' in chemical reactions. The present review considers selective methods of organic synthesis suitable for transformation of complex functionalized molecules under mild conditions. Selected key trends in the modern organic synthesis are considered including the preparation of organofluorine compounds, catalytic cross-coupling and oxidative cross-coupling reactions, atom-economic addition reactions, methathesis processes, oxidation and reduction reactions, synthesis of heterocyclic compounds, design of new homogeneous and heterogeneous catalytic systems, application of photocatalysis, scaling up synthetic procedures to industrial level and development of new approaches to investigation of mechanisms of catalytic reactions. The bibliography includes 840 references

  15. Development of new methods in modern selective organic synthesis: preparation of functionalized molecules with atomic precision

    Science.gov (United States)

    Ananikov, V. P.; Khemchyan, L. L.; Ivanova, Yu V.; Bukhtiyarov, V. I.; Sorokin, A. M.; Prosvirin, I. P.; Vatsadze, S. Z.; Medved'ko, A. V.; Nuriev, V. N.; Dilman, A. D.; Levin, V. V.; Koptyug, I. V.; Kovtunov, K. V.; Zhivonitko, V. V.; Likholobov, V. A.; Romanenko, A. V.; Simonov, P. A.; Nenajdenko, V. G.; Shmatova, O. I.; Muzalevskiy, V. M.; Nechaev, M. S.; Asachenko, A. F.; Morozov, O. S.; Dzhevakov, P. B.; Osipov, S. N.; Vorobyeva, D. V.; Topchiy, M. A.; Zotova, M. A.; Ponomarenko, S. A.; Borshchev, O. V.; Luponosov, Yu N.; Rempel, A. A.; Valeeva, A. A.; Stakheev, A. Yu; Turova, O. V.; Mashkovsky, I. S.; Sysolyatin, S. V.; Malykhin, V. V.; Bukhtiyarova, G. A.; Terent'ev, A. O.; Krylov, I. B.

    2014-10-01

    The challenges of the modern society and the growing demand of high-technology sectors of industrial production bring about a new phase in the development of organic synthesis. A cutting edge of modern synthetic methods is introduction of functional groups and more complex structural units into organic molecules with unprecedented control over the course of chemical transformation. Analysis of the state-of-the-art achievements in selective organic synthesis indicates the appearance of a new trend — the synthesis of organic molecules, biologically active compounds, pharmaceutical substances and smart materials with absolute selectivity. Most advanced approaches to organic synthesis anticipated in the near future can be defined as 'atomic precision' in chemical reactions. The present review considers selective methods of organic synthesis suitable for transformation of complex functionalized molecules under mild conditions. Selected key trends in the modern organic synthesis are considered including the preparation of organofluorine compounds, catalytic cross-coupling and oxidative cross-coupling reactions, atom-economic addition reactions, methathesis processes, oxidation and reduction reactions, synthesis of heterocyclic compounds, design of new homogeneous and heterogeneous catalytic systems, application of photocatalysis, scaling up synthetic procedures to industrial level and development of new approaches to investigation of mechanisms of catalytic reactions. The bibliography includes 840 references.

  16. Atmospheric Prebiotic Chemistry and Organic Hazes

    OpenAIRE

    Trainer, Melissa G.

    2013-01-01

    Earth’s atmospheric composition at the time of the origin of life is not known, but it has often been suggested that chemical transformation of reactive species in the atmosphere was a significant source of prebiotic organic molecules. Experimental and theoretical studies over the past half century have shown that atmospheric synthesis can yield molecules such as amino acids and nucleobases, but these processes are very sensitive to gas composition and energy source. Abiotic synthesis of orga...

  17. Nitric Oxide Signaling in Plant Responses to Abiotic Stresses

    Institute of Scientific and Technical Information of China (English)

    Weihua Qiao; LiuMin Fan

    2008-01-01

    Nitric oxide (NO) plays important roles in diverse physiological processes In plants. NO can provoke both beneficial and harmful effects, which depend on the concentration and location of NO in plant cells. This review is focused on NO synthesis and the functions of NO in plant responses to abiotic environmental stresses. Abiotic stresses mostly induce NO production in plants. NO alleviates the harmfulness of reactive oxygen species, and reacts with other target molecules, and regulates the expression of stress responsive genes under various stress conditions.

  18. Rapid, Microwave-Assisted Organic Synthesis of Selective V600EBRAF Inhibitors for Preclinical Cancer Research

    Science.gov (United States)

    Buck, Jason R.; Saleh, Sam; Uddin, Md. Imam; Manning, H. Charles

    2012-01-01

    We report a dramatically improved total synthesis of two highly selective V600EBRAF inhibitors, PLX4720 and PLX4032, that leverages microwave-assisted organic synthesis (MAOS). Compared with previously reported approaches, our novel MAOS method significantly reduces overall reaction time without compromising yield. In addition to providing a gram-scale route to these compounds for preclinical oncology research, we anticipate this approach could accelerate the synthesis of azaindoles in high-throughput, library-based formats. PMID:23180892

  19. From Polymer to Small Organic Molecules: A Tight Relationship between Radical Chemistry and Solid-Phase Organic Synthesis

    Directory of Open Access Journals (Sweden)

    Danilo Mirizzi

    2011-04-01

    Full Text Available Since Gomberg’s discovery of radicals as chemical entities, the interest around them has increased through the years. Nowadays, radical chemistry is used in the synthesis of 75% of all polymers, inevitably establishing a close relationship with Solid-Phase Organic Synthesis. More recently, the interest of organic chemists has shifted towards the application of usual “in-solution” radical chemistry to the solid-phase, ranging from the use of supported reagents for radical reactions, to the development of methodologies for the synthesis of small molecules or potential libraries. The aim of this review is to put in perspective radical chemistry, moving it away from its origin as a synthetic means for solid supports, to becoming a useful tool for the synthesis of small molecules.

  20. Recent Applications of Polymer Supported Organometallic Catalysts in Organic Synthesis

    Directory of Open Access Journals (Sweden)

    Nina Kann

    2010-09-01

    Full Text Available Recent developments concerning the application of polymer supported organometallic reagents in solid phase synthesis are reviewed, with a special focus on methodology for carbon-carbon formation. Examples of reactions that are covered include the classical Suzuki, Sonogashira and Heck coupings, but also aryl amination, epoxide opening, rearrangements, metathesis and cyclopropanation. Applications in the field of asymmetric synthesis are also discussed.

  1. Carbon Isotope Characterization of Organic Intermediaries in Hydrothermal Hydrocarbon Synthesis by Pyrolysis-GC-MS-C-IRMS

    Science.gov (United States)

    Socki, Richard A.; Fu, Qi; Niles, Paul B.

    2010-01-01

    We report results of experiments designed to characterize the carbon isotope composition of intermediate organic compounds produced as a result of mineral surface catalyzed reactions. The impetus for this work stems from recently reported detection of methane in the Martian atmosphere coupled with evidence showing extensive water-rock interaction during Martian history. Abiotic formation by Fischer-Tropsch-type (FTT) synthesis during serpentinization reactions may be one possible process responsible for methane generation on Mars, and measurement of carbon and hydrogen isotopes of intermediary organic compounds can help constrain the origin of this methane. Of particular interest within the context of this work is the isotopic composition of organic intermediaries produced on the surfaces of mineral catalysts (i.e. magnetite) during hydrothermal experiments, and the ability to make meaningful and reproducible isotope measurements. Our isotope measurements utilize a unique analytical technique combining Pyrolysis-Gas Chromatograph-Mass Spectrometry-Combustion-Isotope Ratio Mass Specrometry (Py-GC-MS-C-IRMS). Others have conducted similar pyrolysis-IRMS experiments on low molecular weight organic acids (Dias, et al, Organic Geochemistry, 33 [2002]). Our technique differs in that it carries a split of the pyrolyzed GC-separated product to a Thermo DSQ-II quadrupole mass spectrometer as a means of making qualitative and semi-quantitative compositional measurements of the organic compounds. A sample of carboxylic acid (mixture of C1 through C6) was pyrolyzed at 100 XC and passed through the GC-MS-C-IRMS (combusted at 940 XC). In order to test the reliability of our technique we compared the _13C composition of different molecular weight organic acids (from C1 through C6) extracted individually by the traditional sealed-tube cupric oxide combustion (940 XC) method with the _13C produced by our pyrolysis technique. Our data indicate that an average 4.3. +/-0.5. (V

  2. Abiotic self-replication.

    Science.gov (United States)

    Meyer, Adam J; Ellefson, Jared W; Ellington, Andrew D

    2012-12-18

    functions (including the replication of nucleic acids) to more competent protein enzymes would complete the journey from an abiotic world to the molecular biology we see today.

  3. The CP molecule labyrinth: a paradigm of how endeavors in total synthesis lead to discoveries and inventions in organic synthesis.

    Science.gov (United States)

    Nicolaou, K C; Baran, Phil S

    2002-08-01

    Imagine an artist carving a sculpture from a marble slab and finding gold nuggets in the process. This thought is not a far-fetched description of the work of a synthetic chemist pursuing the total synthesis of a natural product. At the end of the day, he or she will be judged by the artistry of the final work and the weight of the gold discovered in the process. However, as colorful as this description of total synthesis may be, it does not entirely capture the essence of the endeavor, for there is much more to be told, especially with regard to the contrast of frustrating failures and exhilarating moments of discovery. To fully appreciate the often Herculean nature of the task and the rewards that accompany it, one must sense the details of the enterprise behind the scenes. A more vivid description of total synthesis as a struggle against a tough opponent is perhaps appropriate to dramatize these elements of the experience. In this article we describe one such endeavor of total synthesis which, in addition to reaching the target molecule, resulted in a wealth of new synthetic strategies and technologies for chemical synthesis. The total synthesis of the CP molecules is compared to Theseus' most celebrated athlos (Greek for exploit, accomplishment): the conquest of the dreaded Minotaur, which he accomplished through brilliance, skill, and bravery having traversed the famous labyrinth with the help of Ariadne. This story from Greek mythology comes alive in modern synthetic expeditions toward natural products as exemplified by the total synthesis of the CP molecules which serve as a paradigm for modern total synthesis endeavors, where the objectives are discovery and invention in the broader sense of organic synthesis. PMID:12203464

  4. Submillisecond organic synthesis: Outpacing Fries rearrangement through microfluidic rapid mixing.

    Science.gov (United States)

    Kim, Heejin; Min, Kyoung-Ik; Inoue, Keita; Im, Do Jin; Kim, Dong-Pyo; Yoshida, Jun-ichi

    2016-05-01

    In chemical synthesis, rapid intramolecular rearrangements often foil attempts at site-selective bimolecular functionalization. We developed a microfluidic technique that outpaces the very rapid anionic Fries rearrangement to chemoselectively functionalize iodophenyl carbamates at the ortho position. Central to the technique is a chip microreactor of our design, which can deliver a reaction time in the submillisecond range even at cryogenic temperatures. The microreactor was applied to the synthesis of afesal, a bioactive molecule exhibiting anthelmintic activity, to demonstrate its potential for practical synthesis and production. PMID:27151864

  5. Submillisecond organic synthesis: Outpacing Fries rearrangement through microfluidic rapid mixing.

    Science.gov (United States)

    Kim, Heejin; Min, Kyoung-Ik; Inoue, Keita; Im, Do Jin; Kim, Dong-Pyo; Yoshida, Jun-ichi

    2016-05-01

    In chemical synthesis, rapid intramolecular rearrangements often foil attempts at site-selective bimolecular functionalization. We developed a microfluidic technique that outpaces the very rapid anionic Fries rearrangement to chemoselectively functionalize iodophenyl carbamates at the ortho position. Central to the technique is a chip microreactor of our design, which can deliver a reaction time in the submillisecond range even at cryogenic temperatures. The microreactor was applied to the synthesis of afesal, a bioactive molecule exhibiting anthelmintic activity, to demonstrate its potential for practical synthesis and production.

  6. Compartment specific importance of glutathione during abiotic and biotic stress

    Directory of Open Access Journals (Sweden)

    Bernd eZechmann

    2014-10-01

    Full Text Available The tripeptide thiol glutathione (γ-L-glutamyl-L-cysteinyl-glycine is the most important sulfur containing antioxidant in plants and essential for plant defense against abiotic and biotic stress conditions. It is involved in the detoxification of reactive oxygen species, redox signaling, the modulation of defense gene expression and important for the regulation of enzymatic activities. Even though changes in glutathione contents are well documented in plants and its roles in plant defense are well established, still too little is known about its compartment specific importance during abiotic and biotic stress conditions. Due to technical advances in the visualization of glutathione and the redox state of plants through microscopical methods some progress was made in the last few years in studying the importance of subcellular glutathione contents during stress conditions in plants. This review summarizes the data available on compartment specific importance of glutathione in the protection against abiotic and biotic stress conditions such as high light stress, exposure to cadmium, drought, and pathogen attack (Pseudomonas, Botrytis, Tobacco Mosaic Virus. The data will be discussed in connection with the subcellular accumulation of ROS during these conditions and glutathione synthesis which are both highly compartment specific (e.g. glutathione synthesis takes place in chloroplasts and the cytosol. Thus this review will reveal the compartment specific importance of glutathione during abiotic and biotic stress conditions.

  7. Abiotic racemization kinetics of amino acids in marine sediments

    DEFF Research Database (Denmark)

    Steen, Andrew; Jørgensen, Bo Barker; Lomstein, Bente Aagaard

    2013-01-01

    Enantiomeric ratios of amino acids can be used to infer the sources and composition of sedimentary organic matter. Such inferences, however, rely on knowing the rates at which amino acids in sedimentary organic racemize abiotically. Based on a heating experiment, we report Arrhenius parameters...... between different amino acids or depths. These results can be used in conjunction with measurements of sediment age to predict the ratio of D:L amino acids due solely to abiotic racemization of the source material, deviations from which can indicate the abundance and turnover of active microbial...

  8. An Undergraduate Organic Laboratory Project Involving Independent Synthesis of Novel Flavones.

    Science.gov (United States)

    Letcher, R. M.

    1980-01-01

    Describes a synthetic organic laboratory experiment which ensures independence of students but is not excessively demanding of instructor time. Each student is provided with different starting materials to prepare different flavones but use the same general procedure, the "organic synthesis" flavone preparation. Various features of this procedure…

  9. Carbon dioxide capture and use: organic synthesis using carbon dioxide from exhaust gas.

    Science.gov (United States)

    Kim, Seung Hyo; Kim, Kwang Hee; Hong, Soon Hyeok

    2014-01-13

    A carbon capture and use (CCU) strategy was applied to organic synthesis. Carbon dioxide (CO2) captured directly from exhaust gas was used for organic transformations as efficiently as hyper-pure CO2 gas from a commercial source, even for highly air- and moisture-sensitive reactions. The CO2 capturing aqueous ethanolamine solution could be recycled continuously without any diminished reaction efficiency.

  10. Benzothiazines in organic synthesis. An approach to floresolide B

    Science.gov (United States)

    Chen, Yugang; Harmata, Michael

    2011-01-01

    The intramolecular conjugate addition of a sulfoximine carbanion to an α,β-unsaturated ester results in the formation of a benzothiaine bearing a benzylic stereocenter with extremely high fidelity. We have used this methodology to complete a formal total synthesis of the antitumor agent (+)-floresolide B. PMID:21818165

  11. Template-Free Synthesis of Hierarchical Porous Metal-Organic Frameworks

    Energy Technology Data Exchange (ETDEWEB)

    Yue, Yanfeng [ORNL; Qiao, Zhen-an [University of Tennessee, Knoxville (UTK); Fulvio, Pasquale F [ORNL; Dai, Sheng [ORNL; Binder, Andrew J [ORNL; Tian, Chengcheng [ORNL; Nelson, Kimberly M [ORNL; Zhu, Xiang [ORNL

    2013-01-01

    A template-free synthesis of a hierarchical microporous-mesoporous metal-organic framework (MOF) of Zn(II)-2,5-dihydroxy-1,4-benzenedicarboxylate, namely Zn-MOF-74, is reported. The surface morphology and porosity of the bimodal materials can be modified by etching the pore walls with the synthesis solvent under different reaction times and different solvents. This template-free strategy allows for the preparation of stable frameworks with mesopores exceeding 15 nm, which was previously unattained by the synthesis of MOFs by ligand exten-sion method.

  12. Synthesis of (-)-longithorone A: Using organic synthesis to probe a proposed biosynthesis

    OpenAIRE

    Morales, Carl A.; Layton, Mark E.; Shair, Matthew D.

    2004-01-01

    We present a full report of our enantioselective synthesis of (-)-longithorone A (1). The synthesis was designed to test the feasibility of the biosynthetic proposal for 1 put forward by Schmitz involving intermolecular and transannular Diels–Alder reactions of two [12]-paracyclophane quinones. We have found that if the biosynthesis does involve these two Diels–Alder reactions, the intermolecular Diels–Alder reaction likely occurs before the transannular cycloaddition. The intermolecular Diel...

  13. The use of chemistry for the synthesis of inorganic-organic hybrid materials

    OpenAIRE

    Schmidt, Helmut K.

    1989-01-01

    The combination between inorganic and organic polymeric materials on nanometer scale depends strongly on methods for synthesizing inorganic polymeric networks suitable to the thermal stability of organic materials. The sol-gel process as a "soft-chemistry" method has been proved to be a proper tool for building up inorganic network with incorporated organic components. Examples for chemical synthesis and material applications are given.

  14. Discovery, application and protein engineering of Baeyer-Villiger monooxygenases for organic synthesis.

    Science.gov (United States)

    Balke, Kathleen; Kadow, Maria; Mallin, Hendrik; Sass, Stefan; Bornscheuer, Uwe T

    2012-08-21

    Baeyer-Villiger monooxygenases (BVMOs) are useful enzymes for organic synthesis as they enable the direct and highly regio- and stereoselective oxidation of ketones to esters or lactones simply with molecular oxygen. This contribution covers novel concepts such as searching in protein sequence databases using distinct motifs to discover new Baeyer-Villiger monooxygenases as well as high-throughput assays to facilitate protein engineering in order to improve BVMOs with respect to substrate range, enantioselectivity, thermostability and other properties. Recent examples for the application of BVMOs in synthetic organic synthesis illustrate the broad potential of these biocatalysts. Furthermore, methods to facilitate the more efficient use of BVMOs in organic synthesis by applying e.g. improved cofactor regeneration, substrate feed and in situ product removal or immobilization are covered in this perspective.

  15. Preparation and Purification of Zinc Sulphinate Reagents for Organic Synthesis

    Science.gov (United States)

    O’Hara, Fionn; Baxter, Ryan D.; O’Brien, Alexander G.; Collins, Michael R.; Dixon, Janice A.; Fujiwara, Yuta; Ishihara, Yoshihiro; Baran, Phil S.

    2014-01-01

    SUMMARY The present protocol details the synthesis of zinc bis(alkanesulphinate)s that can be used as general reagents for the formation of radical species. The zinc sulphinates described herein have been generated from the corresponding sulphonyl chlorides by treatment with zinc dust. The products may be used crude, or a simple purification procedure may be performed to minimize incorporation of water and zinc chloride. Elemental analysis has been conducted in order to confirm the purity of the zinc sulphinate reagents; reactions with caffeine have also been carried out to verify the reactivity of each batch that has been synthesized. Although the synthesis of the zinc sulphinate salts generally proceeds within 3 h, workup can take up to 24 h and purification can take up to 3 h. Following the steps in this protocol would enable the user to generate a small toolkit of zinc sulphinate reagents over the course of one week. PMID:23640168

  16. Glycosyl Thioimidates as Versatile Building Blocks for Organic Synthesis

    Science.gov (United States)

    Hasty, S. J.

    2013-01-01

    This review discusses the synthesis and application of glycosyl thioimidates in chemical glycosylation and oligosaccharide assembly. Although glycosyl thioimidates include a broad range of compounds, the discussion herein centers on S-benzothiazolyl (SBaz), S-benzoxazolyl (SBox), S-thiazolinyl (STaz), and S-benzimidazolyl (SBiz) glycosides. These heterocyclic moieties have recently emerged as excellent anomeric leaving groups that express unique characteristics for highly diastereoselective glycosylation and help to provide the streamlined access to oligosaccharides. PMID:24288416

  17. Microwave Assisted Synthesis of Some Bioactive 1,8-Naphthyridinyl Heterocycles and Development of New Synthetic Methodologies in Organic Synthesis

    Institute of Scientific and Technical Information of China (English)

    K. Mogilaiah

    2005-01-01

    @@ 1Introduction Organic synthesis is a powerful discipline, which forms the basis for numerous other areas of research in chemistry and chemical biology. Organic chemists and chemical research in general are under great demand to develop environmentally benign technologies for the synthesis of well-defined precursors and target molecules.It is at this juncture that the microwave assisted technique comes into the picture.Microwave assisted organic reactions have blossomed into an important tool with a variety of applications,particularly after the development of Microwave-induced Organic Reaction Enhancement (MORE) chemistry techniques[1-3]. These techniques require open vessels with little or no solvents and are free of the risk of explosion. MORE chemistry reactions are extremely fast, cleaner than conventional reactions and lead to higher atom economy. Because of short time requirement, ease of workability and eco-friendliness, microwaves provide an alternative green approach to environmentally unacceptable procedures using toxic and expensive reagents. Recently, the use of inorganic solid supports as catalysts[4] have been developed for solvent-free reactions resulting in higher selectivity, milder conditions and easy handling. Clay catalyzed organic reactions are gaining importance owing to their inexpensive nature and special catalytic attributes in heterogeneous reactions[5].

  18. Prebiotic organic matter - Possible pathways for synthesis in a geological context

    Science.gov (United States)

    Chang, S.

    1982-01-01

    Models for the accretion of the earth, core formation, differentiation of the planet into core, mantle, crust, and atmosphere, and prebiotic synthesis of organic materials are reviewed. The development of the Haldane-Oparin and Urey models is traced, and the effect of accretion time on the outgassing process and the composition of the consequent atmosphere is examined. Model prebiotic atmospheres are calculated, the extent of equilibration of the primitive atmosphere is studied and the evolution of the atmosphere prior to organic chemical evolution is reviewed. Finally, experimental progress in synthesis of biological monomers and polymers under presumed early earth conditions is covered.

  19. Can soil respiration estimate neglect the contribution of abiotic exchange?

    Institute of Scientific and Technical Information of China (English)

    Xi CHEN; WenFeng WANG; GePing LUO; Hui YE

    2014-01-01

    This study examines the hypothesis that soil respiration can always be interpreted purely in terms of biotic processes, neglecting the contribution of abiotic exchange to CO2 fluxes in alkaline soils of arid areas that characterize 5%of the Earth’s total land surface. Analyses on flux data collected from previous studies suggested reconciling soil respiration as organic (root/microbial respiration) and inorganic (abiotic CO2 exchange) respiration, whose contributions in the total CO2 flux were determined by soil alkaline content. On the basis of utilizing mete-orological and soil data collected from the Xinjiang and Central Asia Scientific Data Sharing Platform, an incorpo-rated model indicated that inorganic respiration represents almost half of the total CO2 flux. Neglecting the abiotic module may result in overestimates of soil respiration in arid alkaline lands, which partly explains the long-sought“missing carbon sink”.

  20. Titania may produce abiotic oxygen atmospheres on habitable exoplanets

    CERN Document Server

    Narita, Norio; Masaoka, Shigeyuki; Kusakabe, Nobuhiko

    2015-01-01

    The search for habitable exoplanets in the Universe is actively ongoing in the field of astronomy. The biggest future milestone is to determine whether life exists on such habitable exoplanets. In that context, oxygen in the atmosphere has been considered strong evidence for the presence of photosynthetic organisms. In this paper, we show that a previously unconsidered photochemical mechanism by titanium(IV) oxide (titania) can produce abiotic oxygen from liquid water under near ultraviolet (NUV) lights on the surface of exoplanets. Titania works as a photocatalyst to dissociate liquid water in this process. This mechanism offers a different source of a possibility of abiotic oxygen in atmospheres of exoplanets from previously considered photodissociation of water vapor in upper atmospheres by extreme ultraviolet (XUV) light. Our order-of-magnitude estimation shows that possible amounts of oxygen produced by this abiotic mechanism can be comparable with or even more than that in the atmosphere of the current ...

  1. Synthesis of Linearly Fused Benzodipyrrole Based Organic Materials.

    Science.gov (United States)

    Vlasselaer, Maarten; Dehaen, Wim

    2016-01-01

    The objective of this review is to give an overview of the synthetic methods to prepare different indolo[3,2-b]carbazoles and similar systems with a potential use in electro-optical devices such as OLEDs (organic light emitting diode), OPVs (organic photovoltaic) and OFETs (organic field effect transistor). Some further modifications to the core units and their implications for specific applications are also discussed. PMID:27322228

  2. Synthesis of Linearly Fused Benzodipyrrole Based Organic Materials.

    Science.gov (United States)

    Vlasselaer, Maarten; Dehaen, Wim

    2016-06-17

    The objective of this review is to give an overview of the synthetic methods to prepare different indolo[3,2-b]carbazoles and similar systems with a potential use in electro-optical devices such as OLEDs (organic light emitting diode), OPVs (organic photovoltaic) and OFETs (organic field effect transistor). Some further modifications to the core units and their implications for specific applications are also discussed.

  3. Synthesis of Linearly Fused Benzodipyrrole Based Organic Materials

    Directory of Open Access Journals (Sweden)

    Maarten Vlasselaer

    2016-06-01

    Full Text Available The objective of this review is to give an overview of the synthetic methods to prepare different indolo[3,2-b]carbazoles and similar systems with a potential use in electro-optical devices such as OLEDs (organic light emitting diode, OPVs (organic photovoltaic and OFETs (organic field effect transistor. Some further modifications to the core units and their implications for specific applications are also discussed.

  4. Synthesis and characterization of waterborne polyurethane/organic clay nanocomposites

    Institute of Scientific and Technical Information of China (English)

    Zai-feng LI; Sheng-jun WANG; Jin-yan LI

    2008-01-01

    Stable waterborne polyurethane/organic clay latex was synthesized by ultrasonically-assisted mixing with different clay content. Fourier transform infrared (FT-IR) spectra showed that the interaction between NH and C=O was enhanced with low content organic clay loaded. X-ray diffraction (XRD) results implied that the layered organic clay was exfoliated and the crystallization of the hard domain in the waterborne polyurethane (WPU) matrix was enhanced. Transmission electron microscopy (TEM) images show that the layered clay was exfoliated by WPU molecule. The tensile test shows that the mechanical prop-erties were improved by loading organic clay and the desired addition was 1 wt.%.

  5. Organic Fuel Synthesis from Atmospheric Carbon Dioxide and Hydrogen Produced from Water by Electrolysis

    Institute of Scientific and Technical Information of China (English)

    David JOHNSTON

    2009-01-01

    Synthesis of organic fuels from cain dioxide and hydrogen is analysed, in terms of energy recovery efficiency, and the required energy input for electrolysis of water. This electrical energy is related to the thermal energy required in a power station. A method is described to recover heat from energy-producing reactions in the fuel synthesis process, which can then be used to reduce the electrical energy requirement for electrolysis. By co-locating the fuel synthesis plant with a thermal power station, primary (thermal) energy can be used to produce high temperature steam, with a lower electrical requirement for electrolytic production of hydrogen. This can make more efficient use of the primary energy than a thermodynamic engine. Comparison is made with alternative fuels, in terms of energy budget, sustainability, carbon dioxide emissions, etc. The energy security benefits of advanced fuel synthesis are also identified.

  6. A new metalation complex for organic synthesis and polymerization reactions

    Science.gov (United States)

    Hirshfield, S. M.

    1971-01-01

    Organometallic complex of N,N,N',N' tetramethyl ethylene diamine /TMEDA/ and lithium acts as metalation intermediate for controlled systhesis of aromatic organic compounds and polymer formation. Complex of TMEDA and lithium aids in preparation of various organic lithium compounds.

  7. Synthesis of Triptorelin Lactate Catalyzed by Lipase in Organic Media

    Science.gov (United States)

    Zhuang, Hong; Wang, Zhi; Wang, Jiaxin; Zhang, Hong; Xun, Erna; Chen, Ge; Yue, Hong; Tang, Ning; Wang, Lei

    2012-01-01

    Triptorelin lactate was successfully synthesized by porcine pancreatic lipase (PPL) in organic solvents. The effects of acyl donor, substrate ratio, organic solvent, temperature, and water activity were investigated. Under the optimum conditions, a yield of 30% for its ester could be achieved in the reaction for about 48 h. PMID:22949842

  8. Synthesis and Application of the Polyether Modified Organic Silicone

    Institute of Scientific and Technical Information of China (English)

    TONG Dong-feng; LIU Jie; ZHAO Chuan-jun

    2014-01-01

    Polyether modified organic silicone was successfully prepared from Eight methyl siloxane, tetramethyl dihydro two siloxane and UPEO. The chemical structure of the Polyether modified organic silicone was characterized by FT-IR. The wettability of treated cotton fabrics was increased. And the softness was improved significantly.

  9. Studies on the use of haloperoxidases in organic synthesis.

    NARCIS (Netherlands)

    Franssen, M.C.R.

    1987-01-01

    The subject of this thesis is the use of haloperoxidases in synthetic organic chemistry. Haloperoxidases are enzymes capable of halogenating a variety of organic compounds. They require hydrogen peroxide and halide ions as cosubstrates. The enzymes operate under mild conditions, compared to conventi

  10. Organic Matter of the Mulhouse Basin, France: A synthesis

    NARCIS (Netherlands)

    Sinninghe Damsté, J.S.; Hofmann, P.; Huc, A.Y.; Carpentier, B.; Schaeffer, P.; Albrecht, P.; Keely, B.J.; Maxwell, J.R.; Leeuw, J.W. de; Leythaeuser, D.

    1993-01-01

    The lower Oligocene evaporite sequence of the Mulhouse Basin (France) contains organic matter-rich marl deposits. These marls display an overall cyclic variation of sedimentation rate, organic carbon content, hydrogen index and selected molecular parameters over a 30 m thick stratigraphic interval.

  11. Synthesis of refractory organic matter in the ionized gas phase of the solar nebula.

    Science.gov (United States)

    Kuga, Maïa; Marty, Bernard; Marrocchi, Yves; Tissandier, Laurent

    2015-06-01

    In the nascent solar system, primitive organic matter was a major contributor of volatile elements to planetary bodies, and could have played a key role in the development of the biosphere. However, the origin of primitive organics is poorly understood. Most scenarios advocate cold synthesis in the interstellar medium or in the outer solar system. Here, we report the synthesis of solid organics under ionizing conditions in a plasma setup from gas mixtures (H2(O)-CO-N2-noble gases) reminiscent of the protosolar nebula composition. Ionization of the gas phase was achieved at temperatures up to 1,000 K. Synthesized solid compounds share chemical and structural features with chondritic organics, and noble gases trapped during the experiments reproduce the elemental and isotopic fractionations observed in primitive organics. These results strongly suggest that both the formation of chondritic refractory organics and the trapping of noble gases took place simultaneously in the ionized areas of the protoplanetary disk, via photon- and/or electron-driven reactions and processing. Thus, synthesis of primitive organics might not have required a cold environment and could have occurred anywhere the disk is ionized, including in its warm regions. This scenario also supports N2 photodissociation as the cause of the large nitrogen isotopic range in the solar system.

  12. Bottom-up synthesis of chiral covalent organic frameworks and their bound capillaries for chiral separation.

    Science.gov (United States)

    Qian, Hai-Long; Yang, Cheng-Xiong; Yan, Xiu-Ping

    2016-07-12

    Covalent organic frameworks (COFs) are a novel class of porous materials, and offer great potential for various applications. However, the applications of COFs in chiral separation and chiral catalysis are largely underexplored due to the very limited chiral COFs available and their challenging synthesis. Here we show a bottom-up strategy to construct chiral COFs and an in situ growth approach to fabricate chiral COF-bound capillary columns for chiral gas chromatography. We incorporate the chiral centres into one of the organic ligands for the synthesis of the chiral COFs. We subsequently in situ prepare the COF-bound capillary columns. The prepared chiral COFs and their bound capillary columns give high resolution for the separation of enantiomers with excellent repeatability and reproducibility. The proposed strategy provides a promising platform for the synthesis of chiral COFs and their chiral separation application.

  13. Harnessing the Power of the Water-Gas Shift Reaction for Organic Synthesis.

    Science.gov (United States)

    Ambrosi, Andrea; Denmark, Scott E

    2016-09-26

    Since its original discovery over a century ago, the water-gas shift reaction (WGSR) has played a crucial role in industrial chemistry, providing a source of H2 to feed fundamental industrial transformations such as the Haber-Bosch synthesis of ammonia. Although the production of hydrogen remains nowadays the major application of the WGSR, the advent of homogeneous catalysis in the 1970s marked the beginning of a synergy between WGSR and organic chemistry. Thus, the reducing power provided by the CO/H2 O couple has been exploited in the synthesis of fine chemicals; not only hydrogenation-type reactions, but also catalytic processes that require a reductive step for the turnover of the catalytic cycle. Despite the potential and unique features of the WGSR, its applications in organic synthesis remain largely underdeveloped. The topic will be critically reviewed herein, with the expectation that an increased awareness may stimulate new, creative work in the area.

  14. Bottom-up synthesis of chiral covalent organic frameworks and their bound capillaries for chiral separation

    Science.gov (United States)

    Qian, Hai-Long; Yang, Cheng-Xiong; Yan, Xiu-Ping

    2016-07-01

    Covalent organic frameworks (COFs) are a novel class of porous materials, and offer great potential for various applications. However, the applications of COFs in chiral separation and chiral catalysis are largely underexplored due to the very limited chiral COFs available and their challenging synthesis. Here we show a bottom-up strategy to construct chiral COFs and an in situ growth approach to fabricate chiral COF-bound capillary columns for chiral gas chromatography. We incorporate the chiral centres into one of the organic ligands for the synthesis of the chiral COFs. We subsequently in situ prepare the COF-bound capillary columns. The prepared chiral COFs and their bound capillary columns give high resolution for the separation of enantiomers with excellent repeatability and reproducibility. The proposed strategy provides a promising platform for the synthesis of chiral COFs and their chiral separation application.

  15. Synthesis of an Isoindoline-Annulated, Tricyclic Sultam Library via Microwave-Assisted, Continuous-Flow Organic Synthesis (MACOS).

    Science.gov (United States)

    Ullah, Farman; Zang, Qin; Javed, Salim; Porubsky, Patrick; Neuenswander, Benjamin; Lushington, Gerald H; Hanson, Paul R; Organ, Michael G

    2012-01-01

    A microwave-assisted, continuous-flow organic synthesis (MACOS) protocol for the synthesis of an isoindoline-annulat-ed, tricyclic sultam library, utilizing a Heck-aza-Michael (HaM) strategy, is reported. This sequence involves a Heck reaction on vi-nylsulfonamides with batch microwave heating followed by a one-pot, sequential intramolecular aza-Michael cyclization/Boc-deprot-ection using MACOS. Subsequent cyclization with either 1,1'-carbonyldiimidazole or chloromethyl pivalate using MACOS provided an array of tricyclic sultams. This efficient three-step protocol requires only a few hours to produce the target sultams starting from simple starting materials. Using this strategy, a 38-member library of isoindoline-annulated sultams was generated in good to excellent overall yields (53-87%).

  16. Synthesis of an Isoindoline-Annulated, Tricyclic Sultam Library via Microwave-Assisted, Continuous-Flow Organic Synthesis (MACOS)

    Science.gov (United States)

    Ullah, Farman; Zang, Qin; Javed, Salim; Porubsky, Patrick; Neuenswander, Benjamin; Lushington, Gerald H.

    2013-01-01

    A microwave-assisted, continuous-flow organic synthesis (MACOS) protocol for the synthesis of an isoindoline-annulat-ed, tricyclic sultam library, utilizing a Heck–aza-Michael (HaM) strategy, is reported. This sequence involves a Heck reaction on vi-nylsulfonamides with batch microwave heating followed by a one-pot, sequential intramolecular aza-Michael cyclization/Boc-deprot-ection using MACOS. Subsequent cyclization with either 1,1′-carbonyldiimidazole or chloromethyl pivalate using MACOS provided an array of tricyclic sultams. This efficient three-step protocol requires only a few hours to produce the target sultams starting from simple starting materials. Using this strategy, a 38-member library of isoindoline-annulated sultams was generated in good to excellent overall yields (53–87%). PMID:24244052

  17. Proton-Coupled Electron Transfer in Organic Synthesis: Fundamentals, Applications, and Opportunities.

    Science.gov (United States)

    Miller, David C; Tarantino, Kyle T; Knowles, Robert R

    2016-06-01

    Proton-coupled electron transfers (PCETs) are unconventional redox processes in which both protons and electrons are exchanged, often in a concerted elementary step. While PCET is now recognized to play a central a role in biological redox catalysis and inorganic energy conversion technologies, its applications in organic synthesis are only beginning to be explored. In this chapter, we aim to highlight the origins, development, and evolution of the PCET processes most relevant to applications in organic synthesis. Particular emphasis is given to the ability of PCET to serve as a non-classical mechanism for homolytic bond activation that is complimentary to more traditional hydrogen atom transfer processes, enabling the direct generation of valuable organic radical intermediates directly from their native functional group precursors under comparatively mild catalytic conditions. The synthetically advantageous features of PCET reactivity are described in detail, along with examples from the literature describing the PCET activation of common organic functional groups.

  18. Proton-Coupled Electron Transfer in Organic Synthesis: Fundamentals, Applications, and Opportunities.

    Science.gov (United States)

    Miller, David C; Tarantino, Kyle T; Knowles, Robert R

    2016-06-01

    Proton-coupled electron transfers (PCETs) are unconventional redox processes in which both protons and electrons are exchanged, often in a concerted elementary step. While PCET is now recognized to play a central a role in biological redox catalysis and inorganic energy conversion technologies, its applications in organic synthesis are only beginning to be explored. In this chapter, we aim to highlight the origins, development, and evolution of the PCET processes most relevant to applications in organic synthesis. Particular emphasis is given to the ability of PCET to serve as a non-classical mechanism for homolytic bond activation that is complimentary to more traditional hydrogen atom transfer processes, enabling the direct generation of valuable organic radical intermediates directly from their native functional group precursors under comparatively mild catalytic conditions. The synthetically advantageous features of PCET reactivity are described in detail, along with examples from the literature describing the PCET activation of common organic functional groups. PMID:27573270

  19. Synthesis and Resolution of the Atropisomeric 1,1'-Bi-2-Naphthol: An Experiment in Organic Synthesis and 2-D NMR Spectroscopy

    Science.gov (United States)

    Mak, Kendrew K. W.

    2004-01-01

    NMR spectroscopy is presented. It is seen that the experiment regarding the synthesis and resolution of 1,1'-Bi-2-naphtol presents a good experiment for teaching organic synthesis and NMR spectroscopy and provides a strategy for obtaining enantiopure compounds from achiral starting materials.

  20. Novel Metal Organic Framework Synthesis for Spacecraft Oxygen Capture Project

    Data.gov (United States)

    National Aeronautics and Space Administration — Busek and University of Utah propose to develop novel metal organic framework (MOF) material to efficiently capture oxygen in spacecraft cabin environment. The...

  1. Synthesis of a Near-Infrared Emitting Squaraine Dye in an Undergraduate Organic Laboratory

    Science.gov (United States)

    Marks, Patrick; Levine, Mindy

    2012-01-01

    Squaraines are a class of organic fluorophores that possess unique photophysical properties, including strong near-infrared absorption and emission. The synthesis of many squaraines involves the condensation of an electron-rich aromatic ring with squaric acid. These reactions are generally refluxed overnight in a benzene-butanol solvent mixture.…

  2. 2005 Nobel Prize in Chemistry: Development of the Olefin Metathesis Method in Organic Synthesis

    Science.gov (United States)

    Casey, Charles P.

    2006-01-01

    The 2005 Nobel Prize in Chemistry was awarded "for the development of the metathesis method in organic synthesis". The discoveries of the laureates provided a chemical reaction used daily in the chemical industry for the efficient and more environmentally friendly production of important pharmaceuticals, fuels, synthetic fibers, and many other…

  3. A Simple Assignment that Enhances Students' Ability to Solve Organic Chemistry Synthesis Problems and Understand Mechanisms

    Science.gov (United States)

    Teixeira, Jennifer; Holman, R. W.

    2008-01-01

    Organic chemistry students typically struggle with the retrosynthetic approach to solving synthesis problems because most textbooks present the chemistry grouped by "reactions of the functional group". In contrast, the retrosynthetic approach requires the student to envision "reactions that yield the functional group". A second challenge is the…

  4. Sustainable utility of magnetically recyclable nano-catalysts in water: Applications in organic synthesis

    Science.gov (United States)

    Magnetically recyclable nano-catalysts and their use in aqueous media is a perfect combination for the development of greener sustainable methodologies in organic synthesis. It is well established that magnetically separable nano-catalysts avoid waste of catalysts or reagents and...

  5. High-throughput synthesis and characterization of nanocrystalline porphyrinic zirconium metal-organic frameworks.

    Science.gov (United States)

    Kelty, M L; Morris, W; Gallagher, A T; Anderson, J S; Brown, K A; Mirkin, C A; Harris, T D

    2016-06-14

    We describe and employ a high-throughput screening method to accelerate the synthesis and identification of pure-phase, nanocrystalline metal-organic frameworks (MOFs). We demonstrate the efficacy of this method through its application to a series of porphyrinic zirconium MOFs, resulting in the isolation of MOF-525, MOF-545, and PCN-223 on the nanoscale.

  6. Synthesis and Hydrogenation of Disubstituted Chalcones: A Guided-Inquiry Organic Chemistry Project

    Science.gov (United States)

    Mohrig, Jerry R.; Hammond, Christina Noring; Schatz, Paul F.; Davidson, Tammy A.

    2009-01-01

    Guided-inquiry experiments offer the same opportunities to participate in the process of science as classical organic qualitative analysis used to do. This three-week guided-inquiry project involves an aldol-dehydration synthesis of a chalcone chosen from a set of nine, followed by a catalytic transfer hydrogenation reaction using ammonium formate…

  7. Metal organic framework synthesis in the presence of surfactants: towards hierarchical MOFs?

    NARCIS (Netherlands)

    Seoane, B.; Dikhtiarenko, A.; Mayoral, A.; Tellez, C.; Coronas,J.; Kapteijn, F.; Gascon, J.

    2015-01-01

    The effect of synthesis pH and H2O/EtOH molar ratio on the textural properties of different aluminium trimesate metal organic frameworks (MOFs) prepared in the presence of the well-known cationic surfactant cetyltrimethylammonium bromide (CTAB) at 120 °C was studied with the purpose of obtaining a M

  8. Interdisciplinary Learning for Chemical Engineering Students from Organic Chemistry Synthesis Lab to Reactor Design to Separation

    Science.gov (United States)

    Armstrong, Matt; Comitz, Richard L.; Biaglow, Andrew; Lachance, Russ; Sloop, Joseph

    2008-01-01

    A novel approach to the Chemical Engineering curriculum sequence of courses at West Point enabled our students to experience a much more realistic design process, which more closely replicated a real world scenario. Students conduct the synthesis in the organic chemistry lab, then conduct computer modeling of the reaction with ChemCad and…

  9. Enzymatic Synthesis of Dipeptide Derivatives Containing Noncoded Amino Acids in Organic Solvents

    Institute of Scientific and Technical Information of China (English)

    YANG,Hong(杨洪); ZHOU,Chuang(周闯); TIAN,Gui-Ling(田桂玲); YE,Yun-Hua(叶蕴华)

    2002-01-01

    A series of dipeptide derivatives containing non-coded amino acis, N-Boc-4-X-Phe-Ala-NHNHNHPh (X= Cl, Br, I, NO2),were synthesized by using thermoase in organic solvents. The physical data were consistent with the same samples prepared by 3-( diethoxyphosphoryloxy)-1, 2, 3-benzotriazin-4 (3H)-one (DEPBT). Influence of different substituted groups of the non-coded amino acids and different organic solvents on the enzymatic peptide synthesis was studied.

  10. Liquid phase oxidation via heterogeneous catalysis organic synthesis and industrial applications

    CERN Document Server

    Clerici, Mario G

    2013-01-01

    Sets the stage for environmentally friendly industrial organic syntheses From basic principles to new and emerging industrial applications, this book offers comprehensive coverage of heterogeneous liquid-phase selective oxidation catalysis. It fully examines the synthesis, characterization, and application of catalytic materials for environmentally friendly organic syntheses. Readers will find coverage of all the important classes of catalysts, with an emphasis on their stability and reusability. Liquid Phase Oxidation via Heterogeneous Catalysis features contributions from an internation

  11. Organic synthesis by quench reactions. [in prebiotic simulation experiment

    Science.gov (United States)

    Park, W. K.; Hochstim, A. R.; Ponnamperuma, C.

    1975-01-01

    Study of the effects of chemical quench reactions on the formation of organic compounds at a water surface under simulated primordial earth conditions. A mixture of gaseous methane and ammonia over a water surface was exposed to an arc discharge between an electrode and the water surface, generating reactive species. Various organic molecules were formed by a subsequent quenching of these species generated on the water surface. The effects of these water-surface quench reactions were assessed by comparing the amounts of synthesized molecules to the amounts which formed during the discharge of an arc above the water level. It is concluded that the quench (or wet) discharge led to faster rates of reactions, higher-molecular-weight organic compounds, and one-order-of-magnitude larger yields than the dry discharge.

  12. The role of ionizing radiation in primordial organic synthesis.

    Science.gov (United States)

    Ponnamperuma, C.; Sweeney, M.

    1971-01-01

    Attempt to reveal how ionizing radiation may have been effective in producing the molecules necessary for life. In examining the sequence of events leading to the appearance of the first organisms the problem is considered in two parts: the formation of the small molecules such as amino acids, purines, pyrimidines, and carbohydrates; and the condensation of these molecules to give rise to polypeptides and polynucleotides. It is concluded that in the accumulation of organic compounds on the early earth ionizing radiation was not only a substantial part of the available energy, but was also an effective form of energy.

  13. Nanogold plasmonic photocatalysis for organic synthesis and clean energy conversion.

    Science.gov (United States)

    Wang, Changlong; Astruc, Didier

    2014-01-01

    This review provides the basic concepts, an overall survey and the state-of-the art of plasmon-based nanogold photocatalysis using visible light including fundamental understanding and major applications to organic reactions and clean energy-conversion systems. First, the basic concepts of localized surface plasmon resonance (LSPR) are recalled, then the major preparation methods of AuNP-based plasmonic photocatalysts are reviewed. The major part of the review is dedicated to the latest progress in the application of nanogold plasmonic photocatalysis to organic transformations and energy conversions, and the proposed mechanisms are discussed. In conclusion, new challenges and perspectives are proposed and analyzed. PMID:25017125

  14. Nanogold plasmonic photocatalysis for organic synthesis and clean energy conversion.

    Science.gov (United States)

    Wang, Changlong; Astruc, Didier

    2014-01-01

    This review provides the basic concepts, an overall survey and the state-of-the art of plasmon-based nanogold photocatalysis using visible light including fundamental understanding and major applications to organic reactions and clean energy-conversion systems. First, the basic concepts of localized surface plasmon resonance (LSPR) are recalled, then the major preparation methods of AuNP-based plasmonic photocatalysts are reviewed. The major part of the review is dedicated to the latest progress in the application of nanogold plasmonic photocatalysis to organic transformations and energy conversions, and the proposed mechanisms are discussed. In conclusion, new challenges and perspectives are proposed and analyzed.

  15. Hybrid biotic/abiotic nanofactory

    Science.gov (United States)

    Choi, H.-J.; Montemagno, C. D.

    2006-03-01

    In vitro biochemical synthesis is considered a major challenge in replicating cellular functions in engineered systems. Presented is the first nanosized hybrid factory where biochemical reactions take place resulting in the production of biomolecules. A cellular ATP synthesis process is reconstructed in vitro within a bubble architecture using engineered artificial organelles. This is the first introduction of biochemical synthesis from a multiprotein polymersome system and the demonstration of complex proteins' stable functionality in an artificial structure. This hybrid system is expected to have wide application in a number of fields ranging from the in vitro investigation of cellular metabolism to the synthesis of a new class of functional materials.

  16. Green chemistry principles in organic compound synthesis and analysis

    Directory of Open Access Journals (Sweden)

    Ruchi Verma

    2014-03-01

    Full Text Available The present review focus on various green chemistry approaches which could be utilized in the organic compounds in practical classes for undergraduate level in comparison of conventional methods. These methods avoid the usage of hazardous substances and are environmental friendly.

  17. Experimental Investigation of Organic Synthesis in Hydrothermal Environments

    Science.gov (United States)

    Shock, Everett L.

    1998-01-01

    The results of the investigation were presented at a Astrobiology Institute General Meeting. Seafloor hydrothermal systems may be the most likely locations on the early Earth for the emergence of life. Because of the disequilibrium inherent in such dynamic, mixing environments, abundant chemical energy would have been available for formation of the building blocks of life. In addition, theoretical studies suggest that organic compounds in these conditions would reach metastable states, due to kinetic barriers to the formation of stable equilibrium products (CO2 and methane). The speciation of organic carbon in metastable states is highly dependent on the oxidation state, pH, temperature, pressure and bulk composition of the system. The goal of our research is to investigate the effects of a number external variables on the formation, transformation, and stability of organic compounds at hydrothermal conditions. We have begun experimental work to attempt to control the oxidation state of simulated hydrothermal systems by using buffers composed of mineral powders and gas mixtures. We are also beginning to test the stability of organic compounds under these conditions.

  18. EFFICIENCY OF THE ORGANIZATION STAFF WORK: SYNTHESIS OF ORGANIZATIONAL BEHAVIOUR

    OpenAIRE

    Stoyanov, La

    2009-01-01

    There have been described several types of workers behaviour and their influence on the productivity in organization. There is presented a number of issues which make it possible to determine the type of staff behavior and possible ways to control this behavior.

  19. Biodiesel Synthesis and Evaluation: An Organic Chemistry Experiment

    Science.gov (United States)

    Bucholtz, Ehren C.

    2007-01-01

    A new lab esterification reaction based on biodiesel preparation and viscosity, which provides a model experience of industrial process to understand oxidation of vicinal alcohols by periodic acid, is presented. This new desertification experiment and periodate analysis of glycerol for the introductory organic chemistry laboratory provides an…

  20. Chemo-enzymatic peptide synthesis and derivatisation using Subtilisin A in anhydrous organic solvents

    OpenAIRE

    Nuijens, T.

    2012-01-01

    In this thesis it is demonstrated that Alcalase and Cal-B in neat organic solvent can perform unique and cost-efficient conversions that are useful in the peptide area. Not only can Alcalase be used to prepare several C-terminally derivatized amino acids and peptides (such as amides, esters and arylamides), this protease is also a very efficient catalyst for peptide bond formation (optionally combined with Cal-B for ester synthesis) or even for fully enzymatic peptide synthesis strategies bas...

  1. Burn injury differentially alters whole-blood and organ glutathione synthesis rates: An experimental model

    Directory of Open Access Journals (Sweden)

    Zhe-Wei Fei

    2013-09-01

    Full Text Available Previous studies from our laboratories revealed a reduced rate of whole-blood (WB glutathione (GSH synthesis in severely burned patients. To determine whether WB GSH metabolism is an indicator of the status of GSH metabolism in one or more of the major organs, we used a burn rabbit model to determine GSH concentrations and rates of synthesis in WB, liver, lungs, kidney, and skeletal muscle. L-[1- 13 C]-cysteine was infused intravenously for 6 h in rabbits at 3 days post-burn and in sham burn controls. WB and organ 13 C-enrichment of cysteine and GSH was determined by gas chromatography/mass spectrometry. Plasma cysteine metabolic flux was increased significantly (P < 0.01 following burn injury. WB, liver, and lung GSH concentrations (P = 0.054, P < 0.05, and P < 0.05, respectively and fractional rates of GSH synthesis (P < 0.05, P< 0.01, and P< 0.05, respectively were reduced at 3 days post-burn. Kidney was unaffected. There also appears to be an increased rate of GSH transport out of the liver after burn injury. Hence, there is a differential impact of burn injury on tissue and organ GSH status, with WB qualitatively reflecting the changes in lung and liver. It will be important to determine whether these changes are due to alterations in the intrinsic capacity for GSH synthesis and/or availability of amino acid precursors of GSH.

  2. Self-healing anticorrosive organic coating based on an encapsulated water reactive silyl ester: synthesis and proof of concept

    NARCIS (Netherlands)

    García, S.J.; Fischer, H.R.; White, P.A.; Mardel, J.; González-García, Y.; Mol, J.M.C.; Hughes, A.E.

    2011-01-01

    In this paper a self-healing anticorrosive organic coating based on an encapsulated water reactive organic agent is presented. A reactive silyl ester is proposed as a new organic reactive healing agent and its synthesis, performance, incorporation into an organic coating and evaluation of self-heali

  3. Synthesis of the Novel Fluoride-containing Organic Silane

    Institute of Scientific and Technical Information of China (English)

    WANG Shuiping; WENG Rui; WANG Chonghui; YANG Ping

    2009-01-01

    A fluoride-containing organic silane was synthesized by the reaction of N-ethyl-N-hydroxy-ethyl perfluorinated octyl sulfonamide(EHPOS),N-β-aminoethyl)-γ-aminopropyl trimethoxy silane(ATS)and cis-butenedioic anhydride(CA).The experimental results show that the yield of product is up to 87%when the molar ratio of EHPOS:CA:ATS is 1:1.05:1.1.EHPOS and CA were maintained at 115℃for 3 hours,then after cooling the reaction solution to 75℃,ATS was added and reacted for an-other 3.5 hours at 145℃.The structure of the productand thermal properties were characterized by Fourier transform infrared(FTIR)and thermogravimetric analysis(TGA),respectively.Results show that fluo-ride-containing organic silane has excellent thermal stability below 185℃.

  4. Synthesis and study of composite organic silica sorption materials

    Directory of Open Access Journals (Sweden)

    Anna Nikolaevna Shipulya

    2016-03-01

    Full Text Available Currently, one of the promising areas of applied chemistry is research and development of composite absorption materials used as sorbents with a wide range of action, as well as media for biologic preparations and drugs. We have performed research on the development of composite organic silica chitosan-silica based materials with certain composition and biochemical action. Silica was used as the main component, and chitosan - as bio-compatible polymer in the composition of the composite sorbent.

  5. Synthesis of levan in water-miscible organic solvents.

    Science.gov (United States)

    Castillo, E; López-Munguía, A

    2004-10-19

    The synthesis of levan using a levansucrase from a strain of Bacillus subtilis was studied in the presence of the water-miscible solvents: acetone, acetonitrile and 2-methyl-2-propanol (2M2P). It was found that while the enzyme activity is only slightly affected by acetone and acetonitrile, 2M2P has an activating effect increasing the total activity 35% in 40-50% (v/v) 2M2P solutions at 30 degrees C. The enzyme is highly stable in water at 30 degrees C; however, incubation in the presence of 15 and 50% (v/v) 2M2P reduced the half-life time to 23.6 and 1.8 days, respectively. This effect is reversed in 83% 2M2P, where a half-life time of 11.8 days is observed. The presence of 2M2P in the system increases the transfer/hydrolysis ratio of levansucrase. As the reaction proceeds with 10% (w/v) sucrose in 50/50 water/2M2P sucrose is converted to levan and an aqueous two-phase system (2M2P/Levan) is formed and more sucrose can be added in a fed batch mode. It is shown that high molecular weight levan is obtained as an hydrogel and may be easily recovered from the reaction medium. However, when high initial sucrose concentrations (40% (w/v) in 50/50 water/2M2P) are used, an aqueous two-phase system (2M2P/sucrose) is induce, where the synthesized levan has a similar molecular weight distribution as in water and remains in solution. PMID:15464614

  6. Synthesis and application of monodisperse oligo(oxyethylene)-grafted polystyrene resins for solid-phase organic synthesis.

    Science.gov (United States)

    Lumpi, Daniel; Braunshier, Christian; Horkel, Ernst; Hametner, Christian; Fröhlich, Johannes

    2014-07-14

    In a preliminary investigation by our group, we found that poly(styrene-oxyethylene) graft copolymers (PS-PEG), for example, TentaGel resins, are advantageous for gel-phase (13)C NMR spectroscopy. Because of the solution-like environment provided by the PS-PEG resins, good spectral quality of the attached moiety can be achieved, which is useful for nondestructive on-resin analysis. The general drawbacks of such resins are low loading capacities and the intense signal in the spectra resulting from the PEG linker (>50 units). Here, we describe the characterization of solvent-dependent swelling and reaction kinetics on a new type of resin for solid-phase organic synthesis (SPOS) that allows an accurate monitoring by gel-phase NMR without the above disadvantages. A series of polystyrene-oligo(oxyethylene) graft copolymers containing monodisperse PEG units (n = 2-12) was synthesized. A strong correlation between the linker (PEG) length and the line widths in the (13)C gel-phase spectra was observed, with a grafted PEG chain of 8 units giving similar results in terms of reactivity and gel-phase NMR monitoring to TentaGel resin. Multistep on-resin reaction sequences were performed to prove the applicability of the resins in solid-phase organic synthesis.

  7. 'Thunder' - Shock waves in pre-biological organic synthesis.

    Science.gov (United States)

    Bar-Nun, A.; Tauber, M. E.

    1972-01-01

    Theoretical study of the gasdynamics and chemistry of lightning-produced shock waves in a postulated primordial reducing atmosphere. It is shown that the conditions are similar to those encountered in a previously performed shock-tube experiment which resulted in 36% of the ammonia in the original mixture being converted into amino acids. The calculations give the (very large) energy rate of about 0.4 cal/sq cm/yr available for amino acid production, supporting previous hypotheses that 'thunder' could have been responsible for efficient large-scale production of organic molecules serving as precursors of life.

  8. Synthesis of Carbon Nanotubes and Volatile Organic Compounds Detection

    Directory of Open Access Journals (Sweden)

    Sobri S.

    2016-01-01

    Full Text Available In this work, the adsorption effect of volatile organic compounds (chloroacetophenone, acetonitrile and hexane towards the change of resistance of CNTs pellet as sensor signal was investigated. CNTs used in this research were synthesized using Floating Catalyst – Chemical Vapor Deposition (FC-CVD method in optimum condition. The synthesized CNTs were characterized using Scanning Electron Microscopy (SEM, Transmission Electron Microscopy (TEM and Raman Spectroscopy. The variation of resistance changes towards the tested gases were recorded using a multimeter. CNTs sensor pellet showed good responses towards the tested gases, however, the sensitivity, response time and recovery time of sensor pellet need to be optimized.

  9. Synthesis and studies of cometary organic matter analogues

    OpenAIRE

    Bouilloud Randriarimanana, Fanomezantsoa M. Michaëlle

    2015-01-01

    Comets are very interesting for planetology as well as for exobiology. On one hand, held in the furthest and coldest regions of our solar system and due to their small size, they might not have been altered since their formation. The study of comets should allow a better understanding of the physic-chemical processes occurring during the Solar system formation. On the other hand, the analysis performed in 1986 on the environment of 1P/Halley showed the presence, in the cometary dust, of organ...

  10. DNA display III. Solid-phase organic synthesis on unprotected DNA.

    Directory of Open Access Journals (Sweden)

    David R Halpin

    2004-07-01

    Full Text Available DNA-directed synthesis represents a powerful new tool for molecular discovery. Its ultimate utility, however, hinges upon the diversity of chemical reactions that can be executed in the presence of unprotected DNA. We present a solid-phase reaction format that makes possible the use of standard organic reaction conditions and common reagents to facilitate chemical transformations on unprotected DNA supports. We demonstrate the feasibility of this strategy by comprehensively adapting solid-phase 9-fluorenylmethyoxycarbonyl-based peptide synthesis to be DNA-compatible, and we describe a set of tools for the adaptation of other chemistries. Efficient peptide coupling to DNA was observed for all 33 amino acids tested, and polypeptides as long as 12 amino acids were synthesized on DNA supports. Beyond the direct implications for synthesis of peptide-DNA conjugates, the methods described offer a general strategy for organic synthesis on unprotected DNA. Their employment can facilitate the generation of chemically diverse DNA-encoded molecular populations amenable to in vitro evolution and genetic manipulation.

  11. Trophic magnification of organic chemicals: A global synthesis

    Science.gov (United States)

    Walters, David; Jardine, T.D.; Cade, Brian S.; Kidd, K.A.; Muir, D.C.G.; Leipzig-Scott, Peter C.

    2016-01-01

    Production of organic chemicals (OCs) is increasing exponentially, and some OCs biomagnify through food webs to potentially toxic levels. Biomagnification under field conditions is best described by trophic magnification factors (TMFs; per trophic level change in log-concentration of a chemical) which have been measured for more than two decades. Syntheses of TMF behavior relative to chemical traits and ecosystem properties are lacking. We analyzed >1500 TMFs to identify OCs predisposed to biomagnify and to assess ecosystem vulnerability. The highest TMFs were for OCs that are slowly metabolized by animals (metabolic rate kM  0.2 day–1). This probabilistic model provides a new global tool for screening existing and new OCs for their biomagnification potential.

  12. Ionic liquids as an electrolyte for the electro synthesis of organic compounds.

    Science.gov (United States)

    Kathiresan, Murugavel; Velayutham, David

    2015-12-25

    The use of ionic liquids (ILs) as a solvent and an electrolyte for electro organic synthesis has been reviewed. To date several ILs exist, however the ILs based on tetraalkylammonium, pyrrolidinium, piperidinium and imidazolium cations with BF4(-), PF6(-), and TFSI anions have been widely used and explored the most. Electro organic synthesis in ionic liquid media leading to the synthesis of a wide range of organic compounds has been discussed. Anodic oxidation or cathodic reduction will generate radical cation or anion intermediates, respectively. These radicals can undergo self coupling or coupling with other molecules yielding organic compounds of interest. The cation of the IL is known to stabilize the radical anion extensively. This stabilization effect has a specific impact on the electrochemical CO2 reduction and coupling to various organics. The relative stability of the intermediates in IL leads to the formation of specific products in higher yields. Electrochemical reduction of imidazolium or thiazolium based ILs generates N-heterocyclic carbenes that have been shown to catalyze a wide range of base or nucleophile catalyzed organic reactions in IL media, an aspect that falls into the category of organocatalysis. Electrochemical fluorination or selective electrochemical fluorination is another fascinating area that delivers selectively fluorinated organic products in Et3N·nHF or Et4NF·nHF adducts (IL) via anodic oxidation. Oxidative polymerization in ILs has been explored the most; although morphological changes were observed compared to the conventional methods, polymers were obtained in good yields and in some cases ILs were used as dopants to improve the desired properties.

  13. Graphene-like single-layered covalent organic frameworks: synthesis strategies and application prospects.

    Science.gov (United States)

    Liu, Xuan-He; Guan, Cui-Zhong; Wang, Dong; Wan, Li-Jun

    2014-10-29

    Two-dimensional (2D) nanomaterials, such as graphene and transition metal chalcogenides, show many interesting dimension-related materials properties. Inspired by the development of 2D inorganic nanomaterials, single-layered covalent organic frameworks (sCOFs), featuring atom-thick sheets and crystalline extended organic structures with covalently bonded building blocks, have attracted great attention in recent years. With their unique graphene-like topological structure and the merit of structural diversity, sCOFs promise to possess novel and designable properties. However, the synthesis of sCOFs with well-defined structures remains a great challenge. Herein, the recent development of the bottom-up synthesis methods of 2D sCOFs, such as thermodynamic equilibrium control methods, growth-kinetics control methods, and surface-assisted covalent polymerization methods, are reviewed. Finally, some of the critical properties and application prospects of these materials are outlined.

  14. A scalable synthesis of a mesoporous metal-organic framework called NU-1000.

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Timothy C.; Vermeulen, Nicolaas A.; Kim, In Soo; Martinson, Alex B. F.; Stoddart, J. Fraser; Hupp, Joseph T.; Farha, Omar K.

    2016-01-01

    The synthesis of NU-1000, a mesoporous metal-organic framework (MOF), can be conducted efficiently on a multigram scale from inexpensive starting materials. NU-1000 has been reported as an excellent candidate for gas separation and catalysis. In particular, it is ideal for the catalytic deactivation of nerve agents and shows great promise as a new generic platform for a wide range of applications. Multiple post-synthetic modification protocols have been developed using NU-1000 as the parent material, making it a potentially useful scaffold for several catalytic applications. The procedure for the preparation of NU-1000 can be scaled up reliably and is suitable for the production of 50 grams of the requisite organic linker and ?? grams of NU-1000. The entire synthesis is performed without purification by column chromatography and can be completed within 10 days.

  15. STUDY OF SYNTHESIS AND CHARACTERIZATION OF METAL-ORGANIC FRAMEWORKS MOF-5 AS HYDROGEN STORAGE MATERIAL

    Directory of Open Access Journals (Sweden)

    Prapti Rahayu

    2016-03-01

    Full Text Available Metal-organic frameworks (MOFs are porous coordination polymer containing bi-or polidentate organic linker coordinated with inorganic part, such as metal oxide cluster or metal cation as node which called as secondary building unit (SBU to form infinite structure. Due to high porosity and surface area, good thermal stability as well as the availability of unsaturated metal center or the linker influence attracts the interaction with gases, thus MOFs have potential to be applied as hydrogen storage material. One type of MOFs that have been widely studied is [Zn4O(benzene-1,4-dicarboxylate3], namely, MOF-5.Various synthesis method have been developed to obtain optimum results. Characterization of MOF-5 from various synthesis method such as crystallinity, capacity, stability, and quantum dot behavior of MOF-5 have been summarized in this review.

  16. Abiotic racemization kinetics of amino acids in marine sediments.

    Science.gov (United States)

    Steen, Andrew D; Jørgensen, Bo Barker; Lomstein, Bente Aa

    2013-01-01

    The ratios of d- versus l-amino acids can be used to infer the sources and composition of sedimentary organic matter. Such inferences, however, rely on knowing the rates at which amino acids in sedimentary organic matter racemize abiotically between the d- and the l-forms. Based on a heating experiment, we report kinetic parameters for racemization of aspartic acid, glutamic acid, serine, and alanine in bulk sediment from Aarhus Bay, Denmark, taken from the surface, 30 cm, and 340 cm depth below seafloor. Extrapolation to a typical cold deep sea sediment temperature of 3°C suggests racemization rate constants of 0.50×10(-5)-11×10(-5) yr(-1). These results can be used in conjunction with measurements of sediment age to predict the ratio of d:l amino acids due solely to abiotic racemization of the source material, deviations from which can indicate the abundance and turnover of active microbial populations.

  17. Solution-Phase Synthesis of Dipeptides: A Capstone Project That Employs Key Techniques in an Organic Laboratory Course

    Science.gov (United States)

    Marchetti, Louis; DeBoef, Brenton

    2015-01-01

    A contemporary approach to the synthesis and purification of several UV-active dipeptides has been developed for the second-year organic laboratory. This experiment exposes students to the important technique of solution-phase peptide synthesis and allows an instructor to highlight the parallel between what they are accomplishing in the laboratory…

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

    Science.gov (United States)

    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…

  19. Enhanced Singlet Oxygen Generation in Oxidized Graphitic Carbon Nitride for Organic Synthesis.

    Science.gov (United States)

    Wang, Hui; Jiang, Shenlong; Chen, Shichuan; Li, Dandan; Zhang, Xiaodong; Shao, Wei; Sun, Xianshun; Xie, Junfeng; Zhao, Zhi; Zhang, Qun; Tian, Yupeng; Xie, Yi

    2016-08-01

    Experimental data reveal that the incorporation of carbonyl groups into polymer matrix can significantly enhance singlet oxygen ((1) O2 ) generation and suppress production of other reactive oxygen species. Excitonic processes investigated by phosphorescence spectroscopy reveal enhanced triplet-exciton generation in the modified g-C3 N4 , which facilitate (1) O2 generation through an energy transfer process. Benefiting from this, the modified g-C3 N4 shows excellent conversion and selectivity in organic synthesis.

  20. A Research Module for the Organic Chemistry Laboratory: Multistep Synthesis of a Fluorous Dye Molecule

    OpenAIRE

    Michael C. Slade; Raker, Jeffrey R.; Kobilka, Brandon; Pohl, Nicola L. B.

    2014-01-01

    A multi-session research-like module has been developed for use in the undergraduate organic teaching laboratory curriculum. Students are tasked with planning and executing the synthesis of a novel fluorous dye molecule and using it to explore a fluorous affinity chromatography separation technique, which is the first implementation of this technique in a teaching laboratory. Key elements of the project include gradually introducing students to the use of the chemical literature to facilitate...

  1. Optimising the synthesis and red–green–blue emission of a simple organic dye

    OpenAIRE

    Sibrian-Vazquez, Martha; Strongin,Robert

    2009-01-01

    Synthetic dyes have been widely used in supramolecular chemistry not only to probe fundamental chemical interactions but also as components of functional materials. Most current efforts in this regard are directed at designing new host systems for the dyes. Herein we report on the study of a versatile new organic fluorophore. We describe a synthesis which affords improved yields in a convenient one pot procedure. Moreover, a simple method for predicting and controlling the dye’s responses to ...

  2. Polyrhythmic Tapping: Examining the Effectiveness of the Strategy of Organizing Rhythmic Structures through Synthesis

    Science.gov (United States)

    Yokus, Hamit; Yokus, Tuba

    2015-01-01

    In this study the strategy of organizing rhythmic structures through synthesis is named, and defined, and its procedures are described. Its effectiveness for teaching the execution of 3:2, 4:3, 8:3, 5:4, and 3:5 polyrhythmic structures is examined and described. Pre-test and Post-test Control Group Design was employed to test the effectiveness of…

  3. Effects of abiotic stress on plants: a systems biology perspective

    OpenAIRE

    Cramer Grant R; Urano Kaoru; Delrot Serge; Pezzotti Mario; Shinozaki Kazuo

    2011-01-01

    Abstract The natural environment for plants is composed of a complex set of abiotic stresses and biotic stresses. Plant responses to these stresses are equally complex. Systems biology approaches facilitate a multi-targeted approach by allowing one to identify regulatory hubs in complex networks. Systems biology takes the molecular parts (transcripts, proteins and metabolites) of an organism and attempts to fit them into functional networks or models designed to describe and predict the dynam...

  4. Design and synthesis of organic-inorganic hybrid capsules for biotechnological applications.

    Science.gov (United States)

    Shi, Jiafu; Jiang, Yanjun; Wang, Xiaoli; Wu, Hong; Yang, Dong; Pan, Fusheng; Su, Yanlei; Jiang, Zhongyi

    2014-08-01

    Organic-inorganic hybrid capsules, which typically possess a hollow lumen and a hybrid wall, have emerged as a novel and promising class of hybrid materials and have attracted enormous attention. In comparison to polymeric capsules or inorganic capsules, the hybrid capsules combine the intrinsic physical/chemical properties of the organic and inorganic moieties, acquire more degrees of freedom to manipulate multiple interactions, create hierarchical structures and integrate multiple functionalities. Thus, the hybrid capsules exhibit superior mechanical strength (vs. polymeric capsules) and diverse functionalities (vs. inorganic capsules), which may give new opportunities to produce high-performance materials. Much effort has been devoted to exploring innovative and effective methods for the synthesis of hybrid capsules that exhibit desirable performance in target applications. This tutorial review firstly presents a brief description of the capsular structure and hybrid materials in nature, then classifies the hybrid capsules into molecule-hybrid capsules and nano-hybrid capsules based upon the size of the organic and inorganic moieties in the capsule wall, followed by a detailed discussion of the design and synthesis of the hybrid capsules. For each kind of hybrid capsule, the state-of-the-art synthesis methods are described in detail and a critical comment is embedded. The applications of these hybrid capsules in biotechnological areas (biocatalysis, drug delivery, etc.) have also been summarized. Hopefully, this review will offer a perspective and guidelines for the future research and development of hybrid capsules.

  5. A short designed semi-aromatic organic nanotube – synthesis, chiroptical characterization, and host properties

    DEFF Research Database (Denmark)

    Wixe, Torbjörn; Christensen, Niels Johan; Lidin, Sven;

    2014-01-01

    The first generation of an organic nanotube based on the enantiomerically pure bicyclo[3.3.1]nonane framework is presented. The helical tube synthesised is the longest to date having its aromatic systems oriented parallel to the axis of propagation (length 26 Å and inner diameter 11 Å according...... to molecular dynamics simulations in chloroform). The synthesis of the tube, a heptamer, is based on a series of Friedländer condensations and the use of pyrido[3,2-d]pyrimidine units as masked 2-amino aldehydes, as a general means to propagate organic tubular structures and the introduction of a methoxy group...

  6. Gold nanoparticle (AuNPs) and gold nanopore (AuNPore) catalysts in organic synthesis.

    Science.gov (United States)

    Takale, Balaram S; Bao, Ming; Yamamoto, Yoshinori

    2014-04-01

    Organic synthesis using gold has gained tremendous attention in last few years, especially heterogeneous gold catalysis based on gold nanoparticles has made its place in almost all organic reactions, because of the robust and green nature of gold catalysts. In this context, gold nanopore (AuNPore) with a 3D metal framework is giving a new dimension to heterogeneous gold catalysts. Interestingly, AuNPore chemistry is proving better than gold nanoparticles based chemistry. In this review, along with recent advances, major discoveries in heterogeneous gold catalysis are discussed.

  7. Integrated process of distillation with side reactors for synthesis of organic acid esters

    Energy Technology Data Exchange (ETDEWEB)

    Panchal, Chandrakant B; Prindle, John C; Kolah, Aspri; Miller, Dennis J; Lira, Carl T

    2015-11-04

    An integrated process and system for synthesis of organic-acid esters is provided. The method of synthesizing combines reaction and distillation where an organic acid and alcohol composition are passed through a distillation chamber having a plurality of zones. Side reactors are used for drawing off portions of the composition and then recycling them to the distillation column for further purification. Water is removed from a pre-reactor prior to insertion into the distillation column. An integrated heat integration system is contained within the distillation column for further purification and optimizing efficiency in the obtaining of the final product.

  8. Fluid-induced organic synthesis in the solar nebula recorded in extraterrestrial dust from meteorites.

    Science.gov (United States)

    Vollmer, Christian; Kepaptsoglou, Demie; Leitner, Jan; Busemann, Henner; Spring, Nicole H; Ramasse, Quentin M; Hoppe, Peter; Nittler, Larry R

    2014-10-28

    Isotopically anomalous carbonaceous grains in extraterrestrial samples represent the most pristine organics that were delivered to the early Earth. Here we report on gentle aberration-corrected scanning transmission electron microscopy investigations of eight (15)N-rich or D-rich organic grains within two carbonaceous Renazzo-type (CR) chondrites and two interplanetary dust particles (IDPs) originating from comets. Organic matter in the IDP samples is less aromatic than that in the CR chondrites, and its functional group chemistry is mainly characterized by C-O bonding and aliphatic C. Organic grains in CR chondrites are associated with carbonates and elemental Ca, which originate either from aqueous fluids or possibly an indigenous organic source. One distinct grain from the CR chondrite NWA 852 exhibits a rim structure only visible in chemical maps. The outer part is nanoglobular in shape, highly aromatic, and enriched in anomalous nitrogen. Functional group chemistry of the inner part is similar to spectra from IDP organic grains and less aromatic with nitrogen below the detection limit. The boundary between these two areas is very sharp. The direct association of both IDP-like organic matter with dominant C-O bonding environments and nanoglobular organics with dominant aromatic and C-N functionality within one unique grain provides for the first time to our knowledge strong evidence for organic synthesis in the early solar system activated by an anomalous nitrogen-containing parent body fluid.

  9. Evidence for organic synthesis in high temperature aqueous media - facts and prognosis

    Science.gov (United States)

    Simoneit, Bernd R. T.

    1995-01-01

    Hydrothermal systems are common along the active tectonic areas of the earth. Potential sites being studied for organic matter alteration and possible organic synthesis are spreading ridges, off-axis systems, back-arc activity, hot spots, volcanism, and subduction. Organic matter alteration, primarily reductive and generally from immature organic detritus, occurs in these high temperature and rapid fluid flow hydrothermal regimes. Hot circulating water (temperature range - warm to greater than 400 C) is responsible for these molecular alterations, expulsion and migration. Compounds that are obviously synthesized are minor components because they are generally masked by the pyrolysis products formed from contemporary natural organic precursors. The reactivity of organic compounds in hot water (200-350 C) has been studied in autoclaves, and supercritical water as a medium for chemistry has also been evaluated. This high temperature aqueous organic chemistry and the strong reducing conditions of the natural systems suggest this as an important route to produce organic compounds on the primitive earth. Thus a better understanding of the potential syntheses of organic compounds in hydrothermal systems will require investigations of the chemistry of condensation, autocatalysis, catalysis and hydrolysis reactions in aqueous mineral buffered systems over a range of temperatures from warm to greater than 400 C.

  10. Fluid-induced organic synthesis in the solar nebula recorded in extraterrestrial dust from meteorites

    Science.gov (United States)

    Vollmer, Christian; Kepaptsoglou, Demie; Leitner, Jan; Busemann, Henner; Spring, Nicole H.; Ramasse, Quentin M.; Hoppe, Peter; Nittler, Larry R.

    2014-01-01

    Isotopically anomalous carbonaceous grains in extraterrestrial samples represent the most pristine organics that were delivered to the early Earth. Here we report on gentle aberration-corrected scanning transmission electron microscopy investigations of eight 15N-rich or D-rich organic grains within two carbonaceous Renazzo-type (CR) chondrites and two interplanetary dust particles (IDPs) originating from comets. Organic matter in the IDP samples is less aromatic than that in the CR chondrites, and its functional group chemistry is mainly characterized by C–O bonding and aliphatic C. Organic grains in CR chondrites are associated with carbonates and elemental Ca, which originate either from aqueous fluids or possibly an indigenous organic source. One distinct grain from the CR chondrite NWA 852 exhibits a rim structure only visible in chemical maps. The outer part is nanoglobular in shape, highly aromatic, and enriched in anomalous nitrogen. Functional group chemistry of the inner part is similar to spectra from IDP organic grains and less aromatic with nitrogen below the detection limit. The boundary between these two areas is very sharp. The direct association of both IDP-like organic matter with dominant C–O bonding environments and nanoglobular organics with dominant aromatic and C–N functionality within one unique grain provides for the first time to our knowledge strong evidence for organic synthesis in the early solar system activated by an anomalous nitrogen-containing parent body fluid. PMID:25288736

  11. Tangled evolutionary processes with commonality and diversity in plastidial glycolipid synthesis in photosynthetic organisms.

    Science.gov (United States)

    Hori, Koichi; Nobusawa, Takashi; Watanabe, Tei; Madoka, Yuka; Suzuki, Hideyuki; Shibata, Daisuke; Shimojima, Mie; Ohta, Hiroyuki

    2016-09-01

    In photosynthetic organisms, the photosynthetic membrane constitutes a scaffold for light-harvesting complexes and photosynthetic reaction centers. Three kinds of glycolipids, namely monogalactosyldiacylglycerol, digalactosyldiacylglycerol, and sulfoquinovosyldiacylglycerol, constitute approximately 80-90% of photosynthetic membrane lipids and are well conserved from tiny cyanobacteria to the leaves of huge trees. These glycolipids perform a wide variety of functions beyond biological membrane formation. In particular, the capability of adaptation to harsh environments through regulation of membrane glycolipid composition is essential for healthy growth and development of photosynthetic organisms. The genome analysis and functional genetics of the model seed plant Arabidopsis thaliana have yielded many new findings concerning the biosynthesis, regulation, and functions of glycolipids. Nevertheless, it remains to be clarified how the complex biosynthetic pathways and well-organized functions of glycolipids evolved in early and primitive photosynthetic organisms, such as cyanobacteria, to yield modern photosynthetic organisms like land plants. Recently, genome data for many photosynthetic organisms have been made available as the fruit of the rapid development of sequencing technology. We also have reported the draft genome sequence of the charophyte alga Klebsormidium flaccidum, which is an intermediate organism between green algae and land plants. Here, we performed a comprehensive phylogenic analysis of glycolipid biosynthesis genes in oxygenic photosynthetic organisms including K. flaccidum. Based on the results together with membrane lipid analysis of this alga, we discuss the evolution of glycolipid synthesis in photosynthetic organisms. This article is part of a Special Issue entitled: Plant Lipid Biology edited by Kent D. Chapman and Ivo Feussner. PMID:27108062

  12. Design, Synthesis and Characterization of Functional Metal-Organic Framework Materials

    KAUST Repository

    Alamer, Badriah

    2015-06-01

    Over the past few decades, vast majority of industrial and academic research throughout the world has witnessed the emergence of materials that can serve as ideal candidates for potential utility in desired applications, and these materials are known as Metal Organic Framework (MOFs). This exceptional new family of porous materials is fabricated by linkage of metal ions or clusters and organic linkers via strong bonds. MOFs have been awarded with remarkable interest and widely studied due to their inherent structural methodology (e.g. use of various metals, expanded library of organic building blocks with different geometry and functionality particularly frameworks designed from carboxylate organic linkers) and unquestionably unique structural and chemical features for many practical applications. (i.e. gas storage/separation, catalysis, drug delivery etc). Simply, metal organic frameworks epitomize the beauty of porous chemical structures. From a design perspective, the introduction of the Molecular Building Block (MBB) approach is actively being pursued pathway by researchers toward the construction of MOFs by employing inorganic building blocks and organic linkers and taking advantage of not only their multiple coordination modes and geometries but also the way in which they are reticulated to generate final framework. In this thesis, research studies will be directed toward (i) the investigation of the relationship between experimental parameters and synthesis of well-known fcu –MOF, (ii) rational design and synthesis of new rare earth (RE) based MOFs, (ii) isoreticular materials based on particular MBB ([M3O(RCO2)6]), M= p-and d-block metals, and (iv) zeolite- like metal organic framework assembled from single-metal ion based MBB ([MN2(CO2)4]) via 2-, 3-,and 4-connected organic linkers. Consequently, the porosity, chemical and thermal stability, and gas sorption properties will be evaluated and detailed.

  13. TECHNOLOGIES OF SYNTHESIS OF ORGANIC SUBSTANCES BY MICROORGANISMS USING WASTE BIODIESEL PRODUCTION

    Directory of Open Access Journals (Sweden)

    Pirog T. P.

    2015-08-01

    Full Text Available We describe here literature and our experimental data concerning microbial synthesis using waste biodiesel production, mono- and dihydric alcohols (1,3-propanediol, 2,3-butanediol, butanol, ethanol, polyols (mannitol, erythritol, arabitol, organic acids (citric, succinic, lactic, glyceric, polymers and compounds with a complex structure (polysaccharides, polyhydroxyalkanoates, surfactants, cephalosporin, cyanocobalamin. In some mentioned cases recombinant producer strains were used. It was shown that due to the presence of potential inhibitors in the composition of technical (crude glycerol (methanol, sodium and potassium salts, the efficiency of synthesis of most microbial products on such a substrate is lower than on the purified glycerol. However, the need of utilization of this toxic waste (storage and processing of crude glycerol is a serious environmental problem due to the high alkalinity and the content of methanol in it, compensates the lower rates of synthesis of the final product. Furthermore, currently considering the volumes of crude glycerol formed during the production of biodiesel, microbial technologies are preferred for its utilization, allowing realizing biosynthesis of practically valuable metabolites in the environment with the highest possible concentration of this waste. Using of crude glycerol as a substrate will reduce the cost of products of microbial synthesis and increase the profitability of biodiesel production.

  14. The effects of bacterial volatile emissions on plant abiotic stress tolerance

    OpenAIRE

    Xiao-min LIU; Zhang, Huiming

    2015-01-01

    Plant growth-promoting rhizobacteria (PGPR) are beneficial plant symbionts that have been successfully used in agriculture to increase seedling emergence, plant weight, crop yield, and disease resistance. Some PGPR strains release volatile organic compounds (VOCs) that can directly and/or indirectly mediate increases in plant biomass, disease resistance, and abiotic stress tolerance. This mini-review focuses on the enhancement of plant abiotic stress tolerance by bacterial VOCs. The review co...

  15. Metal-organic gel templated synthesis of magnetic porous carbon for highly efficient removal of organic dyes.

    Science.gov (United States)

    Wang, Luhuan; Ke, Fei; Zhu, Junfa

    2016-03-21

    Magnetic porous carbon composites are promising materials in various applications, such as adsorbents, supercapacitors and catalyst supports, due to their high surface area, thermal and chemical stability, and easy separation. However, despite the increasing number of reports of magnetic porous carbon composites, the preparation of these materials with environmentally friendly procedures still remains a great challenge. Herein, we report a facile method to prepare a magnetic porous carbon composite with high surface area from a Fe-based metal-organic gel (MOG) template, an extended structure of a metal-organic framework (MOF). The obtained magnetic porous carbon composite was applied to remove organic dyes from an aqueous solution by selecting methyl orange (MO) as a model molecule. It exhibits excellent adsorption capacity (182.82 mg g(-1)), fast adsorption kinetics (8.13 × 10(-3) g mg(-1) min(-1)), and a perfect magnetic separation performance for the MO removal. This study demonstrates a new way to achieve clean synthesis of magnetic porous carbon materials, and opens a new door for the application of MOGs in organic dye removal.

  16. Synthesis of alkyl esters by cutinase in miniemulsion and organic solvent media.

    Science.gov (United States)

    de Barros, Dragana P C; Fonseca, Luís P; Cabral, Joaquim M S; Weiss, Clemens K; Landfester, Katharina

    2009-05-01

    The main objective of this work was studying and testing the nature and influence of reaction media (organic solvent vs. miniemulsion system) on the synthesis of alkyl esters catalyzed by Fusarium solani pisi cutinase. Ester synthesis and cutinase selectivity for different chain length of acids and alcohols (ethyl and hexyl) were evaluated. In iso-octane, after 1 h of reaction, cutinase exhibits rates of esterification between 0.24 micromol x mg(-)1 x min(-1) for ethyl oleate and 1.15 micromol x mg(-)1 x min(-1) for ethyl butyrate, while in a miniemulsion system the rates were from 0.05 for ethyl heptanoate to 0.76 micromol x mg(-1) x min(-1) for ethyl decanoate. The reaction rate for the synthesis of hexyl esters in a miniemulsion system was from 0.19 for hexyl heptanoate to 1.07 micromol x mg(-)1 x min(-1) for hexyl decanoate. High conversion yields of 95% at equilibrium after 8 h of reaction in iso-octane for pentanoic acid (C(5)) with ethanol at equimolar concentration (0.1 M) was achieved. Additionally, this work showed that a significant and unexpected shift in cutinase selectivity occurred towards longer chain length carboxylic acids (C(8)-C(10)) in miniemulsion system as compared to organic solvent (iso-octane) and previous studies in reverse micellar systems. The possibility of working with higher concentration of substrates, without inhibitory effect on the enzyme, was another advantage of the miniemulsion system.

  17. A new era for organic synthesis-highlights of the recent progress

    Institute of Scientific and Technical Information of China (English)

    WU Yikang; WU Yu-Lin

    2007-01-01

    The major progress in organic synthesis since 2005 is briefly surveyed in two parts.The first part deals with some of the most impressive advances in the synthetic methodology,which includes:(1) metal-mediated synthetic reactions,with an emphasis on the olefin metathesis and gold-mediated reactions;(2) free radical-based organic synthesis;(3) synthetic transformations performed in a "one-pot" manner involving either tandem reactions or multicomponent reactions;(4) asymmetric reactions catalyzed by metal and organo-catalysts.The major advances in total synthesis of some complex natural products with significant biological activities are presented in the second part,with detailed illustrations of ten selected molecules,including dragmacidin F,abyssomicin C,11-acetoxy-4-deoxyasbestinin D,pentacycloanammoxic acid,UCS 1025A,(-)-merrilactone A,nigellamine A2,( +)-saxitoxin,and Tamiflu (an artificially designed natural product-like molecule).An array of complicated structures of the natural products synthesized over the last two years is also listed to serve as a convenient lead to the original literature for the prospective interested readers.

  18. Blue green alga mediated synthesis of gold nanoparticles and its antibacterial efficacy against Gram positive organisms

    Energy Technology Data Exchange (ETDEWEB)

    Uma Suganya, K.S. [Centre for Ocean Research, Sathyabama University, Chennai 600 119 (India); Govindaraju, K., E-mail: govindtu@gmail.com [Centre for Ocean Research, Sathyabama University, Chennai 600 119 (India); Ganesh Kumar, V.; Stalin Dhas, T.; Karthick, V. [Centre for Ocean Research, Sathyabama University, Chennai 600 119 (India); Singaravelu, G. [Nanoscience Division, Department of Zoology, Thiruvalluvar University, Vellore 632115 (India); Elanchezhiyan, M. [Department of Microbiology, Dr ALM Post Graduate Institute of Basic Medical Sciences, University of Madras, Chennai 600113 (India)

    2015-02-01

    Biofunctionalized gold nanoparticles (AuNPs) play an important role in design and development of nanomedicine. Synthesis of AuNPs from biogenic materials is environmentally benign and possesses high bacterial inhibition and bactericidal properties. In the present study, blue green alga Spirulina platensis protein mediated synthesis of AuNPs and its antibacterial activity against Gram positive bacteria is discussed. AuNPs were characterized using Ultraviolet–visible (UV–vis) spectroscopy, Fluorescence spectroscopy, Fourier Transform-Infrared (FTIR) spectroscopy, Raman spectroscopy, High Resolution-Transmission Electron Microscopy (HR-TEM) and Energy Dispersive X-ray analysis (EDAX). Stable, well defined AuNPs of smaller and uniform shape with an average size of ∼ 5 nm were obtained. The antibacterial efficacy of protein functionalized AuNPs were tested against Gram positive organisms Bacillus subtilis and Staphylococcus aureus. - Highlights: • Size controlled synthesis of gold nanoparticles from blue green alga Spirulina platensis • Stability of gold nanoparticles at different temperatures • Potent antibacterial efficacy against Gram positive organisms.

  19. Controlled synthesis of organic nanophotonic materials with specific structures and compositions.

    Science.gov (United States)

    Cui, Qiu Hong; Zhao, Yong Sheng; Yao, Jiannian

    2014-10-29

    Organic nanomaterials have drawn great interest for their potential applications in high-speed miniaturized photonic integration due to their high photoluminescence quantum efficiency, structural processability, ultrafast photoresponse, and excellent property engineering. Based on the rational design on morphological and componential levels, a series of organic nanomaterials have been controllably synthesized in recent years, and their excitonic/photonic behaviors has been fine-tuned to steer the light flow for specific optical applications. This review presents a comprehensive summary of recent breakthroughs in the controlled synthesis of organic nanomaterials with specific structures and compositions, whose tunable photonic properties would provide a novel platform for multifunctional applications. First, we give a general overview of the tailored construction of novel nanostructures with various photonic properties. Then, we summarize the design and controllable synthesis of composite materials for the modulation of their functionalities. Subsequently, special emphasis is put on the fabrication of complex nanostructures towards wide applications in isolated photonic devices. We conclude with our personal viewpoints on the development directions in the novel design and controllable construction of organic nanomaterials for future applications in highly integrated photonic devices and chips.

  20. Synthesis of Vitamin E Succinate from Candida rugosa Lipase in Organic Medium

    Institute of Scientific and Technical Information of China (English)

    JIANG Xiang-jun; HU Yi; JIANG Ling; GONG Ji-hong; HUANG He

    2013-01-01

    A screening of commercially available lipases for the synthesis of vitamin E succinate showed that lipase from Candida rugosa presented the highest yield.The synthesis of vitamin E succinate in organic solvents with different lgP values ranging from-1.3 to 3.5 was investigated.Of particular interest was that dimethyl sulfoxide (DMSO) with the lowest lgP exhibited the highest yield among all the organic solvents used.It suggests that lgP is incapable of satisfactorily predicting the biocompatibility of organic solvents due to the complexity of enzymatic reaction with hydrophilic and hydrophobic substrates in organic solvent.Effects of different operating conditions,such as molar ratio of substrate,enzyme concentration,reaction temperature,mass transfer,and reaction time were also studied.Under the optimum conditions of 10 g/L enzyme,a stirring rate of 100 r/min,a substrate molar ratio of 5:1 at 55 C for 18 h,a satisfactory yield(46.95%) was obtained.The developed method has a potential to be used for efficient enzymatic production of vitamin E succinate.

  1. sp(2)-sp(3) diboranes: astounding structural variability and mild sources of nucleophilic boron for organic synthesis.

    Science.gov (United States)

    Dewhurst, Rian D; Neeve, Emily C; Braunschweig, Holger; Marder, Todd B

    2015-06-14

    Despite the widespread use of organoborane reagents in organic synthesis and catalysis, a major challenge still remains: very few boron-centered nucleophiles exist for the direct construction of B-C bonds. Perhaps the most promising emerging solution to this problem is the use of sp(2)-sp(3) diboranes, in which one boron atom of a conventional diborane(4) is quaternised by either a neutral or anionic nucleophile. These compounds, either isolated or generated in situ, serve as relatively mild and convenient sources of the boryl anion [BR2](-) for use in organic synthesis and have already proven their efficacy in metal-free as well as metal-catalysed borylation reactions. This Feature article documents the history of sp(2)-sp(3) diborane synthesis, their properties and surprising structural variability, and their burgeoning utility in organic synthesis.

  2. Metal organic framework-mediated synthesis of highly active and stable Fischer-Tropsch catalysts.

    Science.gov (United States)

    Santos, Vera P; Wezendonk, Tim A; Jaén, Juan José Delgado; Dugulan, A Iulian; Nasalevich, Maxim A; Islam, Husn-Ubayda; Chojecki, Adam; Sartipi, Sina; Sun, Xiaohui; Hakeem, Abrar A; Koeken, Ard C J; Ruitenbeek, Matthijs; Davidian, Thomas; Meima, Garry R; Sankar, Gopinathan; Kapteijn, Freek; Makkee, Michiel; Gascon, Jorge

    2015-01-01

    Depletion of crude oil resources and environmental concerns have driven a worldwide research on alternative processes for the production of commodity chemicals. Fischer-Tropsch synthesis is a process for flexible production of key chemicals from synthesis gas originating from non-petroleum-based sources. Although the use of iron-based catalysts would be preferred over the widely used cobalt, manufacturing methods that prevent their fast deactivation because of sintering, carbon deposition and phase changes have proven challenging. Here we present a strategy to produce highly dispersed iron carbides embedded in a matrix of porous carbon. Very high iron loadings (>40 wt %) are achieved while maintaining an optimal dispersion of the active iron carbide phase when a metal organic framework is used as catalyst precursor. The unique iron spatial confinement and the absence of large iron particles in the obtained solids minimize catalyst deactivation, resulting in high active and stable operation. PMID:25740709

  3. Synthesis and hydrogen-storage behavior of metal-organic framework MOF-5

    Energy Technology Data Exchange (ETDEWEB)

    Li, Jinping; Zhao, Qiang; Long, Peipei; Dong, Jinxiang [Research Institute of Special Chemicals, Taiyuan University of Technology, Taiyuan 030024, Shanxi (China); Cheng, Shaojuan [Department of Environmental and Chemical Engineering, Luoyang Institute of Science and Technology, Luoyang, Henan 471023 (China)

    2009-02-15

    Metal-organic framework MOF-5 (Zn{sub 4}O(BDC){sub 3}), a microporous material with a high surface area and large pore volume, was synthesized by three approaches: direct mixing of triethylamine (TEA), slow diffusion of TEA, and solvothermal synthesis. The obtained materials were characterized by X-ray diffraction, scanning electron microscopy, thermogravimetric analysis, and nitrogen adsorption, and their hydrogen-storage capacities were measured. The different synthesis methods influenced the pore-structure parameters, morphologies and hydrogen-storage behavior of the obtained MOF-5. MOF-5 synthesized by the solvothermal approach showed a higher surface area and larger pore volume than the samples prepared by the other two approaches. Measurements of the hydrogen-storage behavior showed that the hydrogen-storage capacity was correlated with the specific surface area and pore volume of MOF-5. (author)

  4. Modulation by Amino Acids: Toward Superior Control in the Synthesis of Zirconium Metal-Organic Frameworks.

    Science.gov (United States)

    Gutov, Oleksii V; Molina, Sonia; Escudero-Adán, Eduardo C; Shafir, Alexandr

    2016-09-12

    The synthesis of zirconium metal-organic frameworks (Zr MOFs) modulated by various amino acids, including l-proline, glycine, and l-phenylalanine, is shown to be a straightforward approach toward functional-group incorporation and particle-size control. High yields in Zr-MOF synthesis are achieved by employing 5 equivalents of the modulator at 120 °C. At lower temperatures, the method provides a series of Zr MOFs with increased particle size, including many suitable for single-crystal X-ray diffraction studies. Furthermore, amino acid modulators can be incorporated at defect sites in Zr MOFs with an amino acid/ligand ratio of up to 1:1, depending on the ligand structure and reaction conditions. The MOFs obtained through amino acid modulation exhibit an improved CO2 -capture capacity relative to nonfunctionalized materials.

  5. Little Thermodynamic Penalty for the Synthesis of Ultraporous Metal Organic Frameworks.

    Science.gov (United States)

    Akimbekov, Zamirbek; Navrotsky, Alexandra

    2016-02-16

    Many metal-organic frameworks (MOFs) of ultrahigh porosity (with molar volumes more than ten times greater than those of the corresponding dense phases) have been synthesized. However, the number of possible structures far exceeds those that have been made. It is logical to ask if there are energetic barriers to the stability of ultraporous MOFs or whether there is little thermodynamic penalty to their formation. Herein, we show that although the molar volumes of MOF-177 and UMCM-1 reach ultrahigh values, their energetic metastability is in the same range (of 7-36 kJ mol(-1)) as that seen previously for other porous materials. These findings suggest that there is little thermodynamic penalty for the synthesis of structures with varying porosity, and hence, ultraporous frameworks are energetically accessible. Therefore, innovative synthesis methods have the possibility to overcome the drawbacks of conventional approaches and greatly extend the number, porosity, and properties of new framework materials.

  6. Involvement of Histone Modifications in Plant Abiotic Stress Responses

    Institute of Scientific and Technical Information of China (English)

    Lianyu Yuan; Xuncheng Liu; Ming Luo; Songguang Yang; Keqiang Wu

    2013-01-01

    As sessile organisms, plants encounter various environmental stimuli including abiotic stresses during their lifecycle. To survive under adverse conditions, plants have evolved intricate mechanisms to perceive external signals and respond accordingly. Responses to various stresses largely depend on the plant capacity to modulate the transcriptome rapidly and specifically. A number of studies have shown that the molecular mechanisms driving the responses of plants to environmental stresses often depend on nucleosome histone post-translational modifications including histone acetylation, methylation, ubiquitination, and phosphorylation. The combined effects of these modifications play an essential role in the regulation of stress responsive gene expression. In this review, we highlight our current understanding of the epigenetic mechanisms of histone modifications and their roles in plant abiotic stress response.

  7. Arbuscular mycorrhizal fungal responses to abiotic stresses: A review.

    Science.gov (United States)

    Lenoir, Ingrid; Fontaine, Joël; Lounès-Hadj Sahraoui, Anissa

    2016-03-01

    The majority of plants live in close collaboration with a diversity of soil organisms among which arbuscular mycorrhizal fungi (AMF) play an essential role. Mycorrhizal symbioses contribute to plant growth and plant protection against various environmental stresses. Whereas the resistance mechanisms induced in mycorrhizal plants after exposure to abiotic stresses, such as drought, salinity and pollution, are well documented, the knowledge about the stress tolerance mechanisms implemented by the AMF themselves is limited. This review provides an overview of the impacts of various abiotic stresses (pollution, salinity, drought, extreme temperatures, CO2, calcareous, acidity) on biodiversity, abundance and development of AMF and examines the morphological, biochemical and molecular mechanisms implemented by AMF to survive in the presence of these stresses. PMID:26803396

  8. Genes Acting on Transcriptional Control during Abiotic Stress Responses

    Directory of Open Access Journals (Sweden)

    Glacy Jaqueline da Silva

    2014-01-01

    Full Text Available Abiotic stresses are the major cause of yield loss in crops around the world. Greater genetic gains are possible by combining the classical genetic improvement with advanced molecular biology techniques. The understanding of mechanisms triggered by plants to meet conditions of stress is of fundamental importance for the elucidation of these processes. Current genetically modified crops help to mitigate the effects of these stresses, increasing genetic gains in order to supply the agricultural market and the demand for better quality food throughout the world. To obtain safe genetic modified organisms for planting and consumption, a thorough grasp of the routes and genes that act in response to these stresses is necessary. This work was developed in order to collect important information about essential TF gene families for transcriptional control under abiotic stress responses.

  9. Microwave-Assisted Organic Synthesis in the Organic Teaching Lab: A Simple, Greener Wittig Reaction

    Science.gov (United States)

    Martin, Eric; Kellen-Yuen, Cynthia

    2007-01-01

    A greener, microwave-assisted Wittig reaction has been developed for the second-semester organic teaching laboratory. Utilizing this microwave technique, a variety of styrene derivatives have been successfully synthesized from aromatic aldehydes in good yields (41-68%). The reaction not only occurs under neat reaction conditions, but also employs…

  10. Changes in biotic and abiotic processes following mangrove clearing

    Science.gov (United States)

    Granek, Elise; Ruttenberg, Benjamin I.

    2008-12-01

    Mangrove forests, important tropical coastal habitats, are in decline worldwide primarily due to removal by humans. Changes to mangrove systems can alter ecosystem properties through direct effects on abiotic factors such as temperature, light and nutrient supply or through changes in biotic factors such as primary productivity or species composition. Despite the importance of mangroves as transitional habitats between land and sea, little research has examined changes that occur when they are cleared. We examined changes in a number of biotic and abiotic factors following the anthropogenic removal of red mangroves ( Rhizophora mangle) in the Panamanian Caribbean, including algal biomass, algal diversity, algal grazing rates, light penetration, temperature, sedimentation rates and sediment organic content. In this first study examining multiple ecosystem-level effects of mangrove disturbance, we found that areas cleared of mangroves had higher algal biomass and richness than intact mangrove areas. This increase in algal biomass and richness was likely due to changes in abiotic factors (e.g. light intensity, temperature), but not biotic factors (fish herbivory). Additionally the algal and cyanobacterial genera dominating mangrove-cleared areas were rare in intact mangroves and included a number of genera that compete with coral for space on reefs. Interestingly, sedimentation rates did not differ between intact and cleared areas, but the sediments that accumulated in intact mangroves had higher organic content. These findings are the first to demonstrate that anthropogenic clearing of mangroves changes multiple biotic and abiotic processes in mangrove forests and that some of these changes may influence adjacent habitats such as coral reefs and seagrass beds. Additional research is needed to further explore the community and ecosystem-level effects of mangrove clearing and their influence on adjacent habitats, but it is clear that mangrove conservation is an

  11. A Research Module for the Organic Chemistry Laboratory: Multistep Synthesis of a Fluorous Dye Molecule.

    Science.gov (United States)

    Slade, Michael C; Raker, Jeffrey R; Kobilka, Brandon; Pohl, Nicola L B

    2014-01-14

    A multi-session research-like module has been developed for use in the undergraduate organic teaching laboratory curriculum. Students are tasked with planning and executing the synthesis of a novel fluorous dye molecule and using it to explore a fluorous affinity chromatography separation technique, which is the first implementation of this technique in a teaching laboratory. Key elements of the project include gradually introducing students to the use of the chemical literature to facilitate their searching, as well as deliberate constraints designed to force them to think critically about reaction design and optimization in organic chemistry. The project also introduces students to some advanced laboratory practices such as Schlenk techniques, degassing of reaction mixtures, affinity chromatography, and microwave-assisted chemistry. This provides students a teaching laboratory experience that closely mirrors authentic synthetic organic chemistry practice in laboratories throughout the world.

  12. A Research Module for the Organic Chemistry Laboratory: Multistep Synthesis of a Fluorous Dye Molecule

    Science.gov (United States)

    2014-01-01

    A multi-session research-like module has been developed for use in the undergraduate organic teaching laboratory curriculum. Students are tasked with planning and executing the synthesis of a novel fluorous dye molecule and using it to explore a fluorous affinity chromatography separation technique, which is the first implementation of this technique in a teaching laboratory. Key elements of the project include gradually introducing students to the use of the chemical literature to facilitate their searching, as well as deliberate constraints designed to force them to think critically about reaction design and optimization in organic chemistry. The project also introduces students to some advanced laboratory practices such as Schlenk techniques, degassing of reaction mixtures, affinity chromatography, and microwave-assisted chemistry. This provides students a teaching laboratory experience that closely mirrors authentic synthetic organic chemistry practice in laboratories throughout the world. PMID:24501431

  13. Metal-organic frameworks: structure, properties, methods of synthesis and characterization

    Science.gov (United States)

    Butova, V. V.; Soldatov, M. A.; Guda, A. A.; Lomachenko, K. A.; Lamberti, C.

    2016-03-01

    This review deals with key methods of synthesis and characterization of metal-organic frameworks (MOFs). The modular structure affords a wide variety of MOFs with different active metal sites and organic linkers. These compounds represent a new stage of development of porous materials in which the pore size and the active site structure can be modified within wide limits. The set of experimental methods considered in this review is sufficient for studying the short-range and long-range order of the MOF crystal structure, determining the morphology of samples and elucidating the processes that occur at the active metal site in the course of chemical reactions. The interest in metal-organic frameworks results, first of all, from their numerous possible applications, ranging from gas separation and storage to chemical reactions within the pores. The bibliography includes 362 references.

  14. Effects of dissolved organic matter on the growth and pigments synthesis of Spirulina platensis ( Arthrospira )

    Institute of Scientific and Technical Information of China (English)

    MA Zengling; GAO Kunshan; WATANABE Teruo

    2006-01-01

    Excessive accumulation of dissolved organic matter (DOM) in the culture ponds of Spirulina platensis is usually considered to be one of the potential factors affecting the production of S. platensis, however, we are not quite aware of effects of DOM on the growth and pigments synthesis of S. platensis. In the present study, S. platensis was grown in batch or semi-continuous cultures using the filtrate in the culture ponds that had not been renewed for years. It was found that disssolved organic carbon up to 60 mg/L did not bring about an inhibitory effect on the growth of S. platensis, but increased the contents of chlorophyll a and phycocyanin instead. However, further accumulation of dissolved organic matter could decrease the content of chlorophyll a.

  15. The transition from abiotic to biotic chemistry: When and where?

    Science.gov (United States)

    Bada, J. L.

    2001-12-01

    /product molecules survived long enough to be part of the reaction chain although most researchers who have advanced this scenario favor hydrothermal temperatures. Of the various reactions that have so far been proposed and investigated none have been demonstrated to be autocatalytic. In addition, the reactions are probably not unique to hydrothermal temperatures and would also occur at lower temperatures albeit at slower rates. Based on the estimated Arrhenius activation energies for the synthesis/decomposition reactions of the reactant/product molecules it is likely that they would have been more favorable at lower temperatures. This stability argument is especially important as the autocatalytic reactions advanced to the point of synthesizing informational molecules such as nucleic acids which have very short life times at elevated temperatures. Thus even "metabolic life" as it evolved into biochemistry as we know it would likely only have been feasible if the early Earth was cool. If the transition from abiotic chemistry to biochemistry on the early Earth indeed required cool temperatures, the transition could have occurred during cold, quiescent periods between large bolide impacts. The first life that arose, regardless of the process, may not have survived subsequent bolide impacts, however. Life may have originated several times before surface conditions became tranquil enough for periods sufficiently long to permit the survival and evolution of the first living entities into the first cellular organisms found in the fossil record 3.5 billion years ago. 1. C. Wills and J. L. Bada, 2000. "The Spark of Life: Darwin and the Primeval Soup" (Perseus Publishing, Cambridge MA) 291 pp.

  16. Phenotyping for Abiotic Stress Tolerance in Maize

    Institute of Scientific and Technical Information of China (English)

    Benhilda Masuka; Jose Luis Araus; Biswanath Das; Kai Sonder; Jill E. Cairns

    2012-01-01

    The ability to quickly develop germplasm having tolerance to several complex polygenic inherited abiotic and biotic stresses combined is critical to the resilience of cropping systems in the face of climate change.Molecular breeding offers the tools to accelerate cereal breeding; however,suitable phenotyping protocols are essential to ensure that the much-anticipated benefits of molecular breeding can be realized.To facilitate the full potential of molecular tools,greater emphasis needs to be given to reducing the within-experimental site variability,application of stress and characterization of the environment and appropriate phenotyping tools.Yield is a function of many processes throughout the plant cycle,and thus integrative traits that encompass crop performance over time or organization level (i.e.canopy level) will provide a better alternative to instantaneous measurements which provide only a snapshot of a given plant process.Many new phenotyping tools based on remote sensing are now available including non-destructive measurements of growth-related parameters based on spectral reflectance and infrared thermometry to estimate plant water status.Here we describe key field phenotyping protocols for maize with emphasis on tolerance to drought and low nitrogen.

  17. Abiotic Racemization Kinetics of Amino Acids in Marine Sediments

    OpenAIRE

    Steen, Andrew D.; Bo Barker Jørgensen; Bente Aa Lomstein

    2013-01-01

    The ratios of d- versus l-amino acids can be used to infer the sources and composition of sedimentary organic matter. Such inferences, however, rely on knowing the rates at which amino acids in sedimentary organic matter racemize abiotically between the d- and the l-forms. Based on a heating experiment, we report kinetic parameters for racemization of aspartic acid, glutamic acid, serine, and alanine in bulk sediment from Aarhus Bay, Denmark, taken from the surface, 30 cm, and 340 cm depth be...

  18. Tetracene dicarboxylic imide and its disulfide: synthesis of ambipolar organic semiconductors for organic photovoltaic cells.

    Science.gov (United States)

    Okamoto, Toshihiro; Suzuki, Tsuyoshi; Tanaka, Hideyuki; Hashizume, Daisuke; Matsuo, Yutaka

    2012-01-01

    We have designed and synthesized a new donor/acceptor-type tetracene derivative by the introduction of dicarboxylic imide and disulfide groups as electron-withdrawing and -donating units, respectively. The prepared compounds, tetracene dicarboxylic imide (TI) and its disulfide (TIDS) have high chemical and electrochemical stability as well as long-wavelength absorptions of up to 886 nm in the thin films. The crystal packing structure of TIDS molecules features face-to-face π-stacking, derived from dipole-dipole interactions. Notably, TIDS exhibited ambipolar properties of both electron-donating and -accepting natures in p-n and p-i-n heterojunction organic thin-film photovoltaic devices. Accordingly, TI and TIDS are expected to be promising compounds for designing new organic semiconductors.

  19. Scalable synthesis and post-modification of a mesoporous metal-organic framework called NU-1000.

    Science.gov (United States)

    Wang, Timothy C; Vermeulen, Nicolaas A; Kim, In Soo; Martinson, Alex B F; Stoddart, J Fraser; Hupp, Joseph T; Farha, Omar K

    2016-01-01

    The synthesis of NU-1000, a highly robust mesoporous (containing pores >2 nm) metal-organic framework (MOF), can be conducted efficiently on a multigram scale from inexpensive starting materials. Tetrabromopyrene and (4-(ethoxycarbonyl)phenyl)boronic acid can easily be coupled to prepare the requisite organic strut with four metal-binding sites in the form of four carboxylic acids, while zirconyl chloride octahydrate is used as a precursor for the well-defined metal oxide clusters. NU-1000 has been reported as an excellent candidate for the separation of gases, and it is a versatile scaffold for heterogeneous catalysis. In particular, it is ideal for the catalytic deactivation of nerve agents, and it shows great promise as a new generic platform for a wide range of applications. Multiple post-synthetic modification protocols have been developed using NU-1000 as the parent material, making it a potentially useful scaffold for several catalytic applications. The procedure for the preparation of NU-1000 can be scaled up reliably, and it is suitable for the production of 50 g of the tetracarboxylic acid containing organic linker and 200 mg-2.5 g of NU-1000. The entire synthesis is performed without purification by column chromatography and can be completed within 10 d. PMID:26678084

  20. Scalable synthesis and post-modification of a mesoporous metal-organic framework called NU-1000.

    Science.gov (United States)

    Wang, Timothy C; Vermeulen, Nicolaas A; Kim, In Soo; Martinson, Alex B F; Stoddart, J Fraser; Hupp, Joseph T; Farha, Omar K

    2016-01-01

    The synthesis of NU-1000, a highly robust mesoporous (containing pores >2 nm) metal-organic framework (MOF), can be conducted efficiently on a multigram scale from inexpensive starting materials. Tetrabromopyrene and (4-(ethoxycarbonyl)phenyl)boronic acid can easily be coupled to prepare the requisite organic strut with four metal-binding sites in the form of four carboxylic acids, while zirconyl chloride octahydrate is used as a precursor for the well-defined metal oxide clusters. NU-1000 has been reported as an excellent candidate for the separation of gases, and it is a versatile scaffold for heterogeneous catalysis. In particular, it is ideal for the catalytic deactivation of nerve agents, and it shows great promise as a new generic platform for a wide range of applications. Multiple post-synthetic modification protocols have been developed using NU-1000 as the parent material, making it a potentially useful scaffold for several catalytic applications. The procedure for the preparation of NU-1000 can be scaled up reliably, and it is suitable for the production of 50 g of the tetracarboxylic acid containing organic linker and 200 mg-2.5 g of NU-1000. The entire synthesis is performed without purification by column chromatography and can be completed within 10 d.

  1. Synthesis, properties and self-organization of meso-arylporphyrins with higher alkyl substituents

    Science.gov (United States)

    Bragina, N. A.; Zhdanova, K. A.; Mironov, A. F.

    2016-05-01

    The review summarizes published data on the methods for preparation of meso-arylporphyrins with higher alkyl substituents. The methods for creation of self-organized nanostructures based on these compounds and the data on their applications are presented. Approaches to the synthesis of functionalized lipophilic and amphiphilic meso-arylporphyrins are discussed. The ways and driving forces for the formation of supramolecular porphyrin arrays in solutions and on the substrate surface are considered. The prospects of using alkyl porphyrin derivatives for the design of nanomaterials are shown. The bibliography includes 204 references.

  2. Interface modification and material synthesis of organic light-emitting diodes using plasma technology

    Science.gov (United States)

    Liang, Rongqing; Ou, Qiongrong; Yang, Cheng; He, Kongduo; Yang, Xilu; Zhong, Shaofeng; plasma application Team

    2015-09-01

    Organic light-emitting diodes (OLEDs), due to their unique properties of solution processability, compatibility with flexible substrates and with large-scale printing technology, attract huge interest in the field of lighting. The integration of plasma technology into OLEDs provides a new route to improve their performance. Here we demonstrate the modification of indium-tin-oxide (ITO) work function by plasma treatment, synthesis of thermally activated delayed fluorescence (TADF) materials using plasma grafting (polymerisation), and multi-layer solution processing achieved by plasma cross-linking.

  3. Innovative Catalysis in Organic Synthesis Oxidation, Hydrogenation, and C-X Bond Forming Reactions

    CERN Document Server

    Andersson, Pher G

    2012-01-01

    Authored by a European team of leaders in the field, this book compiles innovative approaches for C-X bond forming processes frequently applied in organic synthesis. It covers all key types of catalysis, including homogeneous, heterogeneous, and organocatalysis, as well as mechanistic and computational studies. Special attention is focused on the improvement of efficiency and sustainability of important catalytic processes, such as selective oxidations, hydrogenation and cross-coupling reactions.The result is a valuable resource for both advanced researchers in academia and industry, as well a

  4. Zeolite-like metal–organic frameworks (ZMOFs): design, synthesis, and properties

    KAUST Repository

    Eddaoudi, Mohamed

    2014-10-24

    This review highlights various design and synthesis approaches toward the construction of ZMOFs, which are metal–organic frameworks (MOFs) with topologies and, in some cases, features akin to traditional inorganic zeolites. The interest in this unique subset of MOFs is correlated with their exceptional characteristics arising from the periodic pore systems and distinctive cage-like cavities, in conjunction with modular intra- and/or extra-framework components, which ultimately allow for tailoring of the pore size, pore shape, and/or properties towards specific applications.

  5. Nobel Prize in Chemistry. Development of the Olefin Metathesis Method in Organic Synthesis

    Science.gov (United States)

    Casey, Charles P.

    2006-02-01

    The 2005 Nobel Prize in Chemistry was awarded to Yves Chauvin of the Institut Français du Pétrole, Robert H. Grubbs of CalTech, and Richard R. Schrock of MIT "for development of the metathesis method in organic synthesis". The discoveries of the laureates provided a chemical reaction now used daily in the chemical industry for the efficient and more environmentally friendly production of important pharmaceuticals, fuels, synthetic fibers, and many other products. This article tells the story of how olefin metathesis became a truly useful synthetic transformation and a triumph for mechanistic chemistry, and illustrates the importance of fundamental research. See JCE Featured Molecules .

  6. [Synthesis and applications of chiral metal-organic framework in the selective separation of enantiomers].

    Science.gov (United States)

    Qi, Xiaoyue; Li, Xianjiang; Bai, Yu; Liu, Huwei

    2016-01-01

    Chirality is a universal phenomenon in nature. Chiral separation is vitally important in drug development, agricultural chemistry, pharmacology, environmental science, biology and many other fields. Chiral metal-organic frameworks (MOFs) are a new group of porous materials with special topology and designable pore structures, as well as their high specific surface area, porosity, excellent thermal stability, solvent resistance, etc. Thus, chiral MOFs are promising with various applications in the field of analytical chemistry. This review summarizes the synthesis strategies of chiral MOFs and their applications in the selective separation of enantiomers, as well as related mechanism.

  7. Applications of Continuous-Flow Photochemistry in Organic Synthesis, Material Science, and Water Treatment.

    Science.gov (United States)

    Cambié, Dario; Bottecchia, Cecilia; Straathof, Natan J W; Hessel, Volker; Noël, Timothy

    2016-09-14

    Continuous-flow photochemistry in microreactors receives a lot of attention from researchers in academia and industry as this technology provides reduced reaction times, higher selectivities, straightforward scalability, and the possibility to safely use hazardous intermediates and gaseous reactants. In this review, an up-to-date overview is given of photochemical transformations in continuous-flow reactors, including applications in organic synthesis, material science, and water treatment. In addition, the advantages of continuous-flow photochemistry are pointed out and a thorough comparison with batch processing is presented.

  8. Synthesis of zinc oxide nanocrystals by thermal decomposition of Zn-oleate in organic medium

    Institute of Scientific and Technical Information of China (English)

    Beng; S.ONG; Rafik; O.LOUTFY

    2008-01-01

    We report the synthesis of uniform-sized hexagonal ZnO nanocrystals by the thermolysis of Zn-oleate complex,which was prepared from the reaction of inexpensive and environmentally friendly reagents such as zinc nitrate and sodium oleate.Two organic compounds with different boiling points,octadecene and octylether,were selected as the medium for thermolysis of Zn-oleate complex.Under optimized reaction conditions,we were able to synthesize ZnO nanoparticles with the size being about 10 nm.X-ray diffraction and transmission electron micrograph(TEM) images confirmed the high crystallinity of the nanocrystals.

  9. Synthesis of zinc oxide nanocrystals by thermal decomposition of Zn-oleate in organic medium

    Institute of Scientific and Technical Information of China (English)

    LI ChenSha; LI YuNing; WU YiLiang; Beng S. ONG; Rafik O. LOUTFY

    2008-01-01

    We report the synthesis of uniform-sized hexagonal ZnO nanocrystals by the thermolysis of Zn-oleate complex, which was prepared from the reaction of inex-pensive and environmentally friendly reagents such as zinc nitrate and sodium oleate. Two organic compounds with different boiling points, octadecene and oc-tylether, were selected as the medium for thermolysis of Zn-oleate complex. Under optimized reaction conditions, we were able to synthesize ZnO nanoparticles with the size being about 10 nm. X-ray diffraction and transmission electron micrograph (TEM) images confirmed the high crystallinity of the nanocrystals.

  10. Lifetimes of organic photovoltaics: Design and synthesis of single oligomer molecules in order to study chemical degradation mechanisms

    DEFF Research Database (Denmark)

    Alstrup, J.; Norrman, K.; Jørgensen, M.;

    2006-01-01

    Degradation mechanisms in organic and polymer photovoltaics are addressed through the study of an organic photovoltaic molecule based on a single phenylene-vinylene-type oligomer molecule. The synthesis of such a model compound with different end-groups is presented that allows for assignment...

  11. Benign by design: catalyst-free in-water, on-water green chemical methodologies in organic synthesis

    Science.gov (United States)

    The development of organic synthesis under sustainable conditions is a primary goal of practicing green chemists who want to prevent pollution and design safer pathways. Although, it is challenging to avoid the use of catalysts, or solvents in all the organic reactions but progre...

  12. A Student-Centered First-Semester Introductory Organic Laboratory Curriculum Facilitated by Microwave-Assisted Synthesis (MAOS)

    Science.gov (United States)

    Russell, Cianán B.; Mason, Jeremy D.; Bean, Theodore G.; Murphree, S. Shaun

    2014-01-01

    An instructional laboratory curriculum for a first-semester introductory organic chemistry course has been developed using microwave-assisted organic synthesis (MAOS). Taking advantage of short reaction times, materials were developed to facilitate collaborative experimental design, analysis, and debriefing of results during the normal laboratory…

  13. Protein synthesis evaluation in brain and other organs in human by PET

    International Nuclear Information System (INIS)

    The choice of treatment in diseases of the nervous system cannot be based only on symptomatology, but on a presumed underlying pathological state. These pathological states often involve direct modifications of neuronal metabolism. Two areas of cellular biochemistry can be studied in vivo in humans: 1) glucose or oxygen consumption which is mainly responsible for energy and lipid metabolism. 2) amino acid metabolism, which is involved in protein and neurotransmitter synthesis. Here the authors examine protein synthesis, which is the basis of cellular integrity and tissue structure. Study of protein synthesis (PS) by positron emission tomography (PET) is governed by specific requirements dictated by 1) the metabolic pathways we want to explore (the fate of the tracer directly influences the analysis of the results); 2) The construction and validation of a mathematical model to be applied to the computerized images; and 3) the human pathology being studied. The timing of scanning and the experimental protocol must include in their conception some physiological constraints such as volume of organs, rapidity of biological phenomena, etc. All these steps are detailed in the following paragraphs

  14. Metal-Organic Framework Synthesis System Based on Fuzzy Predictive Control via Network Transmission

    Directory of Open Access Journals (Sweden)

    Jui-Ho Chen

    2014-01-01

    Full Text Available The purpose of this study is to construct metal-organic framework (MOF synthesis heating systems based on fuzzy method for monitoring and automatic control. In this study, the temperature sensing module for measurements sensed values that it through a wireless ZigBee chips and wired DAQ device for real-time data transmission. Because MOF synthesis, often due to different modes of heating or heating instability caused by its nucleation and crystal growth rate, is an important influence, leading to different crystallinity, the use of fuzzy theory to predict the temperature parameter and instant heating MOF synthesis parameters can be adjusted to improve the accuracy of the system. The research system to RS-232 interface module for infrared emission control packets issued and automated control of the furnace through the infrared receiver module. This study is based on a terminal interface window of Visual Basic programming and LabView graphical diagram for control system design. Finally, this research, through a number of experiments to validate the use of fuzzy system development methods and networks, can improve the accuracy of the reaction efficiency MOF sensing and control the heating system.

  15. Parameters Affecting the Synthesis of (Z)-3-hexen-1-yl acetate by Transesterifacation in Organic Solvent

    International Nuclear Information System (INIS)

    (Z)-3-hexen-1-yl esters are important green top-note components of food flavors and fragrances. Crude acetone powders extracted lipases from five plant seedlings of rapeseed, wheat, barley, linseed and maize were investigated for their use in the synthesis of flavor esters with vinyl acetate by transesterification in organic solvents. Rape seedlings showed the highest degree of (Z)-3-hexen-1-yl acetate synthesis with a yield of 76 percentage in 72 h. Rape seedling was chosen as promising biocatalyst to evaluate the effects of some of reaction parameters on (Z)-3-hexen-1-yl acetate synthesis using vinyl acetate and (Z)-3-hexen-1-ol at 40 Degree C in n-hexane with 50 g/L enzyme as catalyst. Acetonitrile proved distinctly superior solvent. The percent remaining activity relative to fresh seedlings powders was highest in wheat and barley. Highest ester yield of 80 percentage was obtained with 0.8 M of substrate concentrations within 48 h. Crude rapeseed lipase afforded a conversion 93 percentage of ethyl alcohol. Higher ester yield was achieved within first 24 h with added molecular. The crude rape seedlings lipase is low cost yet effective, showed potential for the production of green note esters industrially. (author)

  16. Synthesis of magnetic metal-organic framework (MOF) for efficient removal of organic dyes from water

    Science.gov (United States)

    Zhao, Xiaoli; Liu, Shuangliu; Tang, Zhi; Niu, Hongyun; Cai, Yaqi; Meng, Wei; Wu, Fengchang; Giesy, John P.

    2015-07-01

    A novel, simple and efficient strategy for fabricating a magnetic metal-organic framework (MOF) as sorbent to remove organic compounds from simulated water samples is presented and tested for removal of methylene blue (MB) as an example. The novel adsorbents combine advantages of MOFs and magnetic nanoparticles and possess large capacity, low cost, rapid removal and easy separation of the solid phase, which makes it an excellent sorbent for treatment of wastewaters. The resulting magnetic MOFs composites (also known as MFCs) have large surface areas (79.52 m2 g-1), excellent magnetic response (14.89 emu g-1), and large mesopore volume (0.09 cm3 g-1), as well as good chemical inertness and mechanical stability. Adsorption was not drastically affected by pH, suggesting π-π stacking interaction and/or hydrophobic interactions between MB and MFCs. Kinetic parameters followed pseudo-second-order kinetics and adsorption was described by the Freundlich isotherm. Adsorption capacity was 84 mg MB g-1 at an initial MB concentration of 30 mg L-1, which increased to 245 mg g-1 when the initial MB concentration was 300 mg L-1. This capacity was much greater than most other adsorbents reported in the literature. In addition, MFC adsorbents possess excellent reusability, being effective after at least five consecutive cycles.

  17. Abiotic Deposition of Fe Complexes onto Leptothrix Sheaths.

    Science.gov (United States)

    Kunoh, Tatsuki; Hashimoto, Hideki; McFarlane, Ian R; Hayashi, Naoaki; Suzuki, Tomoko; Taketa, Eisuke; Tamura, Katsunori; Takano, Mikio; El-Naggar, Mohamed Y; Kunoh, Hitoshi; Takada, Jun

    2016-01-01

    Bacteria classified in species of the genus Leptothrix produce extracellular, microtubular, Fe-encrusted sheaths. The encrustation has been previously linked to bacterial Fe oxidases, which oxidize Fe(II) to Fe(III) and/or active groups of bacterial exopolymers within sheaths to attract and bind aqueous-phase inorganics. When L. cholodnii SP-6 cells were cultured in media amended with high Fe(II) concentrations, Fe(III) precipitates visibly formed immediately after addition of Fe(II) to the medium, suggesting prompt abiotic oxidation of Fe(II) to Fe(III). Intriguingly, these precipitates were deposited onto the sheath surface of bacterial cells as the population was actively growing. When Fe(III) was added to the medium, similar precipitates formed in the medium first and were abiotically deposited onto the sheath surfaces. The precipitates in the Fe(II) medium were composed of assemblies of globular, amorphous particles (ca. 50 nm diameter), while those in the Fe(III) medium were composed of large, aggregated particles (≥3 µm diameter) with a similar amorphous structure. These precipitates also adhered to cell-free sheaths. We thus concluded that direct abiotic deposition of Fe complexes onto the sheath surface occurs independently of cellular activity in liquid media containing Fe salts, although it remains unclear how this deposition is associated with the previously proposed mechanisms (oxidation enzyme- and/or active group of organic components-involved) of Fe encrustation of the Leptothrix sheaths. PMID:27271677

  18. Titania may produce abiotic oxygen atmospheres on habitable exoplanets

    Science.gov (United States)

    Narita, Norio; Enomoto, Takafumi; Masaoka, Shigeyuki; Kusakabe, Nobuhiko

    2015-12-01

    The search for habitable exoplanets in the Universe is actively ongoing in the field of astronomy. The biggest future milestone is to determine whether life exists on such habitable exoplanets. In that context, oxygen in the atmosphere has been considered strong evidence for the presence of photosynthetic organisms. In this paper, we show that a previously unconsidered photochemical mechanism by titanium (IV) oxide (titania) can produce abiotic oxygen from liquid water under near ultraviolet (NUV) lights on the surface of exoplanets. Titania works as a photocatalyst to dissociate liquid water in this process. This mechanism offers a different source of a possibility of abiotic oxygen in atmospheres of exoplanets from previously considered photodissociation of water vapor in upper atmospheres by extreme ultraviolet (XUV) light. Our order-of-magnitude estimation shows that possible amounts of oxygen produced by this abiotic mechanism can be comparable with or even more than that in the atmosphere of the current Earth, depending on the amount of active surface area for this mechanism. We conclude that titania may act as a potential source of false signs of life on habitable exoplanets.Reference:Narita N. et al.,Scientific Reports 5, Article number: 13977 (2015)http://www.nature.com/articles/srep13977

  19. Polyamines in response to abiotic stress tolerance through transgenic approaches

    Science.gov (United States)

    Pathak, Malabika Roy; Teixeira da Silva, Jaime A; Wani, Shabir H

    2014-01-01

    The distribution, growth, development and productivity of crop plants are greatly affected by various abiotic stresses. Worldwide, sustainable crop productivity is facing major challenges caused by abiotic stresses by reducing the potential yield in crop plants by as much as 70%. Plants can generally adapt to one or more environmental stresses to some extent. Physiological and molecular studies at transcriptional, translational, and transgenic plant levels have shown the pronounced involvement of naturally occurring plant polyamines (PAs), in controlling, conferring, and modulating abiotic stress tolerance in plants. PAs are small, low molecular weight, non-protein polycations at physiological pH, that are present in all living organisms, and that have strong binding capacity to negatively charged DNA, RNA, and different protein molecules. They play an important role in plant growth and development by controlling the cell cycle, acting as cell signaling molecules in modulating plant tolerance to a variety of abiotic stresses. The commonly known PAs, putrescine, spermidine, and spermine tend to accumulate together accompanied by an increase in the activities of their biosynthetic enzymes under a range of environmental stresses. PAs help plants to combat stresses either directly or by mediating a signal transduction pathway, as shown by molecular cloning and expression studies of PA biosynthesis-related genes, knowledge of the functions of PAs, as demonstrated by developmental studies, and through the analysis of transgenic plants carrying PA genes. This review highlights how PAs in higher plants act during environmental stress and how transgenic strategies have improved our understanding of the molecular mechanisms at play. PMID:24710064

  20. Microbiologically produced carboxylic acids used as building blocks in organic synthesis.

    Science.gov (United States)

    Aurich, Andreas; Specht, Robert; Müller, Roland A; Stottmeister, Ulrich; Yovkova, Venelina; Otto, Christina; Holz, Martina; Barth, Gerold; Heretsch, Philipp; Thomas, Franziska A; Sicker, Dieter; Giannis, Athanassios

    2012-01-01

    Oxo- and hydroxy-carboxylic acids are of special interest in organic synthesis. However, their introduction by chemical reactions tends to be troublesome especially with regard to stereoselectivity. We describe herein the biotechnological preparation of selected oxo- and hydroxycarboxylic acids under "green" conditions and their use as promising new building blocks. Thereby, our biotechnological goal was the development of process fundamentals regarding the variable use of renewable raw materials, the development of a multi purpose bioreactor and application of a pilot plant with standard equipment for organic acid production to minimize the technological effort. Furthermore the development of new product isolation procedures, with the aim of direct product recovery, capture of products or single step operation, was necessary. The application of robust and approved microorganisms, also genetically modified, capable of using a wide range of substrates as well as producing a large spectrum of products, was of special importance. Microbiologically produced acids, like 2-oxo-glutaric acid and 2-oxo-D-gluconic acid, are useful educts for the chemical synthesis of hydrophilic triazines, spiro-connected heterocycles, benzotriazines, and pyranoic amino acids. The chiral intermediate of the tricarboxylic acid cycle, (2R,3S)-isocitric acid, is another promising compound. For the first time our process provides large quantities of enantiopure trimethyl (2R,3S)-isocitrate which was used in subsequent chemical transformations to provide new chiral entities for further usage in total synthesis and pharmaceutical research.Oxo- and hydroxy-carboxylic acids are of special interest in organic synthesis. However, their introduction by chemical reactions tends to be troublesome especially with regard to stereoselectivity. We describe herein the biotechnological preparation of selected oxo- and hydroxycarboxylic acids under "green" conditions and their use as promising new building

  1. Sustainable Utility of Magnetically Recyclable Nano-Catalysts in Water: Applications in Organic Synthesis

    Directory of Open Access Journals (Sweden)

    Manoj B. Gawande

    2013-10-01

    Full Text Available Magnetically recyclable nano-catalysts and their use in aqueous media is a perfect combination for the development of greener sustainable methodologies in organic synthesis. It is well established that magnetically separable nano-catalysts avoid waste of catalysts or reagents and it is possible to recover >95% of catalysts, which is again recyclable for subsequent use. Water is the ideal medium to perform the chemical reactions with magnetically recyclable nano-catalysts, as this combination adds tremendous value to the overall benign reaction process development. In this review, we highlight recent developments inthe use of water and magnetically recyclable nano-catalysts (W-MRNs for a variety of organic reactions namely hydrogenation, condensation, oxidation, and Suzuki–Miyaura cross-coupling reactions, among others.

  2. [Emission characteristics and hazard assessment analysis of volatile organic compounds from chemical synthesis pharmaceutical industry].

    Science.gov (United States)

    Li, Yan; Wang, Zhe-Ming; Song, Shuang; Xu, Zhi-Rong; Xu, Ming-Zhu; Xu, Wei-Li

    2014-10-01

    In this study, volatile organic compounds (VOCs) released from chemical synthesis pharmaceutical industry in Taizhou, Zhejiang province were analyzed quantitatively and qualitatively. The total volatile organic compounds (TVOCs) was in the range of 14.9-308.6 mg · m(-3). Evaluation models of ozone formation potentials (OFP) and health risk assessment were adopted to preliminarily assess the environmental impact and health risk of VOCs. The results showed that the values of OFP of VOCs were in the range of 3.1-315.1 mg · m(-3), based on the maximum incremental reactivity, the main principal contribution was toluene, tetrahydrofuran (THF), acetic ether etc. The non-carcinogenic risk and the carcinogen risk fell in the ranges of 9.48 x 10(-7)-4.98 x 10(-4) a(-1) and 3.17 x 10(-5)- 6.33 x 10(-3). The principal contribution of VOCs was benzene, formaldehyde and methylene chloride.

  3. Synthesis and characterization of monodispersed inorganic/organic core/shell microspheres with fluorescence

    Institute of Scientific and Technical Information of China (English)

    ZHANG Kai; HAN Kun; ZHANG Xuehai; YANG Bai

    2005-01-01

    @@ In recent years, the semiconductor nanocrystals (NCs) have attracted great interest due to their potentials in photonics, electronics, magnetics and catalysis, and the monodispersed organic or inorganic microspheres doped NCs display predominant characteristics in the fabrication and study for photonic crystals[1,2], and considerable effort has been devoted to the design and synthesis of CdTe NCs doped colloid with well fluorescence[3-8]. For example, CdTe NCs were fabricated on the surfaces of silica or polymer microspheres by the methods of layer-by-layer assembly, and CdTe NCs were also doped into inorganic or organic microspheres through sol-gel process or swell- ing.

  4. Nanoscale luminescent lanthanide-based metal–organic frameworks: properties, synthesis, and applications

    Energy Technology Data Exchange (ETDEWEB)

    Hu, Dongqin; Song, Yonghai; Wang, Li, E-mail: lwanggroup@aliyun.com [Jiangxi Normal University, Key Laboratory of Functional Small Organic Molecule, Ministry of Education, Key Laboratory of Chemical Biology, Jiangxi Province, College of Chemistry and Chemical Engineering (China)

    2015-07-15

    Nanoscale luminescent lanthanide-based metal–organic frameworks (NLLn-MOFs) possess superior optical and physical properties such as higher luminescent lifetime, quantum yield, high stability, high surface area, high agent loading, and intrinsic biodegradability, and therefore are regarded as a novel generation of luminescent material compared with bulk lanthanide-based metal–organic frameworks (Ln-MOFs). Traditional luminescent Ln-MOFs have been well studied; however, NLLn-MOFs taking the advantages of nanomaterials have attracted extensive investigations for applications in optical imaging in living cells, light-harvesting, and sensing. In this review, we provide a survey of the latest progresses made in developing NLLn-MOFs, which contains the fundamental optical features, synthesis, and their potential applications. Finally, the future prospects and challenges of the rapidly growing field are summarized.

  5. Thiophene fused azacoronenes: regioselective synthesis, self organization, charge transport, and its incorporation in conjugated polymers

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Yi; He, Bo

    2015-09-15

    A regioselective synthesis of an azacoronene fused with two peripheral thiophene groups has been realized through a concise synthetic route. The resulting thienoazacoronene (TAC) derivatives show high degree of self-organization in solution, in single crystals, in the bulk, and in spuncast thin films. Spuncast thin film field-effect transistors of the TACs exhibited mobilities up to 0.028 cm.sup.2V.sup.-1 S.sup.-1, which is among the top field effect mobilities for solution processed discotic materials. Organic photovoltaic devices using TAC-containing conjugated polymers as the donor material exhibited a high open-circuit voltage of 0.89 V, which was ascribable to TAC's low-lying highest occupied molecular orbital energy level.

  6. Templated synthesis of nitrogen-enriched nanoporous carbon materials from porogenic organic precursors prepared by ATRP.

    Science.gov (United States)

    Wu, Dingcai; Li, Zhenghui; Zhong, Mingjiang; Kowalewski, Tomasz; Matyjaszewski, Krzysztof

    2014-04-01

    A facile templated synthesis of functional nanocarbon materials with well-defined spherical mesopores is developed using all-organic porogenic precursors comprised of hairy nanoparticles with nitrogen-rich polyacrylonitrile shells grafted from sacrificial cross-linked poly(methyl methacrylate) cores (xPMMA-g-PAN). Such shape-persistent all-organic nanostructured precursors, prepared using atom transfer radical polymerization (ATRP), assure robust formation of template nanostructures with continuous PAN precursor matrix over wide range of compositions, and allow for removal of the sacrificial template through simple thermal decomposition. Carbon materials prepared using this method combine nitrogen enrichment with hierarchical nanostructure comprised of microporous carbon matrix interspersed with mesopores originating from sacrificial xPMMA cores, and thus perform well as CO2 adsorbents and as supercapacitor electrodes. PMID:24596246

  7. Thiophene fused azacoronenes: regioselective synthesis, self organization, charge transport, and its incorporation in conjugated polymers

    Science.gov (United States)

    Liu, Yi; He, Bo

    2015-09-15

    A regioselective synthesis of an azacoronene fused with two peripheral thiophene groups has been realized through a concise synthetic route. The resulting thienoazacoronene (TAC) derivatives show high degree of self-organization in solution, in single crystals, in the bulk, and in spuncast thin films. Spuncast thin film field-effect transistors of the TACs exhibited mobilities up to 0.028 cm.sup.2V.sup.-1 S.sup.-1, which is among the top field effect mobilities for solution processed discotic materials. Organic photovoltaic devices using TAC-containing conjugated polymers as the donor material exhibited a high open-circuit voltage of 0.89 V, which was ascribable to TAC's low-lying highest occupied molecular orbital energy level.

  8. Confined-Pyrolysis as an Experimental Method for Hydrothermal Organic Synthesis

    Science.gov (United States)

    Leif, Roald N.; Simoneit, Bernd R. T.

    1995-01-01

    A closed pyrolysis system has been developed as a tool for studying the reactions of organic compounds under extreme hydrothermal conditions. Small high pressure stainless steel vessels in which the ratio of sediment or sample to water has been adjusted to eliminate the headspace at peak experimental conditions confines the organic components to the bulk solid matrix and eliminates the partitioning of the organic compounds away from the inorganic components during the experiment. Confined pyrolysis experiments were performed to simulate thermally driven catagenetic changes in sedimentary organic matter using a solids to water ratio of 3.4 to 1. The extent of alteration was measured by monitoring the steroid and triterpenoid biomarkers and polycyclic aromatic hydrocarbon distributions. These pyrolysis experiments duplicated the hydrothermal transformations observed in nature. Molecular probe experiments using alkadienes, alkenes and alkanes in H2O and D2O elucidated the isomerization and hydrogenation reactions of aliphatic and the competing oxidative reactions occurring under hydrothermal conditions. This confined pyrolysis technique is being applied to test experiments on organic synthesis of relevance to chemical evolution for the origin of life.

  9. Overexpression of malate dehydrogenase in transgenic alfalfa enhances organic acid synthesis and confers tolerance to aluminum.

    Science.gov (United States)

    Tesfaye, M; Temple, S J; Allan, D L; Vance, C P; Samac, D A

    2001-12-01

    Al toxicity is a severe impediment to production of many crops in acid soil. Toxicity can be reduced through lime application to raise soil pH, however this amendment does not remedy subsoil acidity, and liming may not always be practical or cost-effective. Addition of organic acids to plant nutrient solutions alleviates phytotoxic Al effects, presumably by chelating Al and rendering it less toxic. In an effort to increase organic acid secretion and thereby enhance Al tolerance in alfalfa (Medicago sativa), we produced transgenic plants using nodule-enhanced forms of malate dehydrogenase and phosphoenolpyruvate carboxylase cDNAs under the control of the constitutive cauliflower mosaic virus 35S promoter. We report that a 1.6-fold increase in malate dehydrogenase enzyme specific activity in root tips of selected transgenic alfalfa led to a 4.2-fold increase in root concentration as well as a 7.1-fold increase in root exudation of citrate, oxalate, malate, succinate, and acetate compared with untransformed control alfalfa plants. Overexpression of phosphoenolpyruvate carboxylase enzyme specific activity in transgenic alfalfa did not result in increased root exudation of organic acids. The degree of Al tolerance by transformed plants in hydroponic solutions and in naturally acid soil corresponded with their patterns of organic acid exudation and supports the concept that enhancing organic acid synthesis in plants may be an effective strategy to cope with soil acidity and Al toxicity. PMID:11743127

  10. Microwave-Assisted Solid Phase Organic Synthesis.Application to Indole Library Construction

    Institute of Scientific and Technical Information of China (English)

    DAI Wei-Min; SUN Li-Ping; GUO Dian-Shun; HUANG Xiang-Hong

    2004-01-01

    Microwave-assisted organic synthesis (MAOS) has attained increasing popularity due to recent advancement in the instrumentation of microwave technology. Now, MAOS can be performed under controlled temperature and pressure to yield reproducible results. For combinatorial chemistry,the dramatically increased reaction rate under microwave irradiation at high temperature provides an ideal solution to those sluggish reactions, in particular the combinatorial reactions carried out on solid supports. In this presentation, we describe our results on microwave-assisted solid-phase organic synthesis (MASPOS) applied to the construction of indole libraries such as 5. Compounds 4 were synthesized on the Rink amide resins using IRORI MicroKanTM reactors encoded with a radio-frequency (Rf) tag. The resin-bound terminal alkynes 2, prepared via the amide bond, were cross-coupled with the nitroaryl triflate under the conditions adopted from the solution reactions developed by us1,2. The nitro group of 3 was then reduced and sulfonylated to give 4. Ring closure reactions within 4 with Cu(OAc)2 were examined initially in refluxing DCE for 24 h, but no indole product was detected after cleavage from the resin. Therefore, the same reactions were carried out under microwave irradiation at 200 ℃ for 10 min on a Personal Chemistry Emrys Creator, the desired indoles 5 were obtained in 60-95% overall yields calculated from 1 and in >90% purities in most cases3. It is necessary to mention that the IRORI microreactors cannot tolerate the high temperature and the resin-bound 4 must be transferred to the reaction vials for the microwave-assisted ring closure reactions. A traceless synthesis of an indole library via MASPOS will be discussed as well.4

  11. Zr-based metal-organic frameworks: design, synthesis, structure, and applications.

    Science.gov (United States)

    Bai, Yan; Dou, Yibo; Xie, Lin-Hua; Rutledge, William; Li, Jian-Rong; Zhou, Hong-Cai

    2016-04-21

    Among the large family of metal-organic frameworks (MOFs), Zr-based MOFs, which exhibit rich structure types, outstanding stability, intriguing properties and functions, are foreseen as one of the most promising MOF materials for practical applications. Although this specific type of MOF is still in its early stage of development, significant progress has been made in recent years. Herein, advances in Zr-MOFs since 2008 are summarized and reviewed from three aspects: design and synthesis, structure, and applications. Four synthesis strategies implemented in building and/or modifying Zr-MOFs as well as their scale-up preparation under green and industrially feasible conditions are illustrated first. Zr-MOFs with various structural types are then classified and discussed in terms of different Zr-based secondary building units and organic ligands. Finally, applications of Zr-MOFs in catalysis, molecule adsorption and separation, drug delivery, and fluorescence sensing, and as porous carriers are highlighted. Such a review based on a specific type of MOF is expected to provide guidance for the in-depth investigation of MOFs towards practical applications.

  12. Tracking of the organic species during the synthesis of cobalt-based nanoparticles in non-aqueous solution

    Science.gov (United States)

    Staniuk, M.; Niederberger, M.; Koziej, D.

    2014-08-01

    In this work we investigate the organic products of the synthesis of Co-based nanoparticles in benzyl alcohol. Our GC and in situ IR studies provide the experimental proofs for the formation of benzaldehyde, toluene and isopropanol in the reaction solution. These organic products can be correlated with formation of cobalt-based nanoparticles with oxidation state from 0 to 3+. These results shine the light on the complexity of organic and inorganic reactions in solution during crystallization of nanoparticles.

  13. Synthesis of nanoporous carbohydrate metal-organic framework and encapsulation of selected organic compounds

    Science.gov (United States)

    Al-Ghamdi, Saleh

    Cyclodextrin metal organic frameworks (CDMOFs) with different types of cyclodextrins (CDs) (i.e., Alpha, Beta and Gamma-CD) and coordination potassium ion sources (KOH) CDMOF-a and (C7H5KO2) CDMOF-b were synthesized and fully characterized. The physical and thermal properties of the successfully produced CDMOFs were evaluated using N2 gas sorption, thermal gravimetric analysis (TGA), X-ray diffraction (XRD), and scanning electron microscopy (SEM). The N2 gas sorption isotherm revealed high uptake into the micropores (330 cm3.g -1 for Gamma-CDMOF-a) to macropore (125 cm3.g -1 for Gamma-CDMOF-b) structures with isotherm types I and II for Gamma-CDMOFs and Alpha-CDMOFs, respectively. The Langmuir specific surface area (SSA) of Gamma-CDMOF-a (1376 m2.g-1) was significantly higher than the SSA of Alpha-CDMOF-a (289 m2.g -1) and Beta-CDMOF-a (54 m2.g-1). The TGA of dehydrated CDMOF crystals showed the structures were thermally stable up to 300 °C. The XRD of the Gamma-CDMOFs and Alpha-CDMOFs showed a highly face-centered-cubic symmetrical structure. An Aldol condensation reaction occurred during the encapsulation of acetaldehyde, hexanal, trans-2-hexenal, and ethanol into Gamma-CDMOF-a, with a SSA of 1416 m2.g -1. However, Gamma-CDMOF-b with a SSA of 499 m2.g -1 was successfully used to encapsulate acetaldehyde. The maximum release of acetaldehyde from CDMOF-b was 53 mug of acetaldehyde per g of CDMOF, which is greater than previously reported acetaldehyde encapsulation on Beta-CD inclusion complexes.

  14. Organic-Stabilizer-Free Polyol Synthesis of Silver Nanowires for Electrode Applications.

    Science.gov (United States)

    Sim, Hwansu; Bok, Shingyu; Kim, Bongsung; Kim, Minha; Lim, Guh-Hwan; Cho, Sung Min; Lim, Byungkwon

    2016-09-19

    The polyol reduction of a Ag precursor in the presence of an organic stabilizer, such as poly(vinylpyrrolidone), is a widely used method for the production of Ag nanowires (NWs). However, organic capping molecules introduce insulating layers around each NW. Herein we demonstrate that Ag NWs can be produced in high yield without any organic stabilizers simply by introducing trace amounts of NaCl and Fe(NO3 )3 during low-temperature polyol synthesis. The heterogeneous nucleation and growth of Ag NWs on initially formed AgCl particles, combined with oxidative etching of unwanted Ag nanoparticles, resulted in the selective formation of long NWs with an average length of about 40 μm in the absence of a capping or stabilizing effect provided by surface-adsorbing molecules. These organic-stabilizer-free Ag NWs were directly used for the fabrication of high-performance transparent or stretchable electrodes without a complicated process for the removal of capping molecules from the NW surface.

  15. Controlled Synthesis of Organic/Inorganic van de Waals Solid for Tunable Light-matter Interactions

    CERN Document Server

    Niu, Lin; Cong, Chunxiao; Wu, Chunyang; Wu, Di; Chang, Tay-Rong; Wang, Hong; Zeng, Qingsheng; Zhou, Jiadong; Wang, Xingli; Fu, Wei; Yu, Peng; Fu, Qundong; Zhang, Zhuhua; Yakobson, Boris I; Tay, Beng Kang; Jeng, Horng-Tay; Lin, Hsin; Sum, Tze Chien; Jin, Chuanhong; He, Haiyong; Yu, Ting; Liu, Zheng

    2015-01-01

    Van de Waals (vdW) solids, as a new type of artificial materials that consisting of alternative layers bonded by weak interactions, have shed light on fantastic optoelectronic devices. As a result, a large variety of shining vdW devices have been engineered via layer-by-layer stacking of two-dimensional materials, although shadowed by the difficulties of fabrication. Alternatively, direct growth of vdW solids have been proved a scalable and swift way towards vdW solids, reflected by the successful synthesis of graphene/h-BN and transition metal dichalcogenides (TMDs) vertical heterostructures from controlled vapor deposition. Enlightened by it, with a three-step deposition and reaction, we realize high-quality organic and inorganic vdW solids, using methylammonium lead halide as the organic part (organic perovskite) and 2D monolayers inorganic as counterpart. Being a perfect light absorbent, the electrons and holes generated in organic perovskite couple with its inorganic 2D companions, and behave dramaticall...

  16. Room-temperature sol–gel synthesis of organic ligand-capped ZnO nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Zobel, Mirijam, E-mail: mirijam.zobel@fau.de; Chatterjee, Haimantee [Friedrich-Alexander University Erlangen-Nürnberg (FAU), Department of Physics, Lehrstuhl für Kristallographie und Strukturphysik (Germany); Matveeva, Galina; Kolb, Ute [Johannes Gutenberg-Universität, Institut für Physikalische Chemie (Germany); Neder, Reinhard B., E-mail: reinhard.neder@fau.de [Friedrich-Alexander University Erlangen-Nürnberg (FAU), Department of Physics, Lehrstuhl für Kristallographie und Strukturphysik (Germany)

    2015-05-15

    Powders of zinc oxide nanoparticles with individual particle sizes below 10 nm in diameter are readily produced in base-induced sol–gel processes from ethanolic solutions of zinc acetate dihydrate. These particles are covered with acetate molecules and without further stabilization, they grow when stored as a powder. Here, we present three organic ligands, which reproducibly stabilize individual particle sizes <5 nm within the agglomerated powders for extended periods of time, up to months. Citric acid and 1,5-diphenyl-1,3,5-pentanetrione result in average diameters of 3 nm, whereas dimethyl-L-tartrate stabilizes 2.1 nm. X-ray diffraction and pair distribution function analysis were used to investigate the structural properties of the particles. TEM data confirm the individual particle size and crystallinity and show that the particles are agglomerated without structural coherence. Besides the introduction of these novel ligands for ZnO nanoparticles, we investigated, in particular, the influence of each synthesis step onto the final nanoparticle size in the powder. Previous studies often reported the employed synthesis parameters, but did not motivate the reasoning for their choice based on detailed experimental observations. Herein, we regard separately the steps of (i) the synthesis of the colloids, (ii) their precipitation, and (iii) the drying of the resulting gel to understand the role of the ligands therein. ZnO particles only covered with acetate grow to 5 nm during the drying process, whereas particles with any of the additional ligands retain their colloidal size of 2–3 nm. This clearly shows the efficient binding and effect of the presented ligands.

  17. Disassembly and reassembly of polyhydroxyalkanoates: recycling through abiotic depolymerization and biotic repolymerization.

    Science.gov (United States)

    Myung, Jaewook; Strong, Nathaniel I; Galega, Wakuna M; Sundstrom, Eric R; Flanagan, James C A; Woo, Sung-Geun; Waymouth, Robert M; Criddle, Craig S

    2014-10-01

    An abiotic-biotic strategy for recycling of polyhydroxyalkanoates (PHAs) is evaluated. Base-catalyzed PHA depolymerization yields hydroxyacids, such as 3-hydroxybutyrate (3HB), and alkenoates, such as crotonate; catalytic thermal depolymerization yields alkenoates. Cyclic pulse addition of 3HB to triplicate bioreactors selected for an enrichment of Comamonas, Brachymonas and Acinetobacter. After each pulse, poly(3-hydroxybutyrate) (P3HB) transiently appeared: accumulation of P3HB correlated with hydrolysis of polyphosphate; consumption of P3HB correlated with polyphosphate synthesis. Cells removed from the cyclic regime and incubated with 3HB under nitrogen-limited conditions produced P3HB (molecular weight>1,000,000Da) at 50% of the cell dry weight (recycling strategy where abiotic depolymerization of waste PHAs yields feedstock for customized PHA re-synthesis appears feasible, without the need for energy-intensive feedstock purification.

  18. Synthesis of Organic Matter of Prebiotic Chemistry at the Protoplanetary Disc

    Science.gov (United States)

    Snytnikov, Valeriy; Stoynovskaya, Olga; Rudina, Nina

    We have carried out scanning electron microscopic examination of CM carbonaceous chondrites meteorites Migey, Murchison, Staroe Boriskino aged more than 4.56 billion years (about 50 million years from the beginning of the formation of the Solar system). Our study confirmed the conclusion of Rozanov, Hoover and other researchers about the presence of microfossils of bacterial origin in the matrix of all these meteorites. Since the time of the Solar system formation is 60 - 100 million years, the primary biocenosis emerged in the protoplanetary disc of the Solar system before meteorites or simultaneously with them. It means that prebiological processes and RNA world appeared even earlier in the circumsolar protoplanetary disc. Most likely, this appearance of prebiotic chemistry takes place nowday in massive and medium-massive discs of the observed young stellar objects (YSO) class 0 and I. The timescale of the transition from chemical to biological evolution took less than 50 million years for the Solar system. Further evolution of individual biocenosis in a protoplanetary disc associated with varying physico-chemical conditions during the formation of the Solar system bodies. Biocenosis on these bodies could remove or develop under the influence of many cosmic factors and geological processes in the case of Earth. To complete the primary biosphere formation in short evolution time - millions of years - requires highly efficient chemical syntheses. In industrial chemistry for the efficient synthesis of ammonia, hydrogen cyanide, methanol and other organic species, that are the precursors to obtain prebiotic compounds, catalytic reactors of high pressure are used. Thus (1) necessary amount of the proper catalyst in (2) high pressure areas of the disc can trigger these intense syntheses. The disc contains the solids with the size from nanoparticle to pebble. Iron and magnesium is catalytically active ingredient for such solids. The puzzle is a way to provide hydrogen

  19. Synthesis of metal-organic framework films by pore diffusion method

    Science.gov (United States)

    Murayama, Naohiro; Nishimura, Yuki; Kajiro, Hiroshi; Kishida, Satoru; Kinoshita, Kentaro; Tottori Univ Team; Nippon Steel; Sumitomo Metal Co. Collaboration; Tottori Integrated Frontier Resaerch Center (Tifrec) Collaboration; Tottori University Electronic Display Resaerch Center (Tedrec) Collaboration

    Metal-organic frameworks (MOFs) presents high controllability in designing the nano-scale pore, and this enable molecular storages, catalysts, gas sensors, gas separation membranes, and electronic devices for next-generation. Therefore, a simple method for film synthesis of MOFs compared with conventional methods [1] is strongly required. In this paper, we provide pore diffusion method, in which a substrate containing constituent metals of MOF is inserted in solution that includes only linker molecules of MOF. As a result, 2D growth of MOF was effectively enhanced, and the formation of flat and dense MOF films was attained. The growth time, t, dependence of film thickness, d, can be expressed by the relation of d = Aln(t + 1) + B, where A and B are constants. It means that ionized coppers diffuse through the pores of MOFs and the synthesis reaction proceeds at the MOF/solvent interface. We demonstrated the fabrication of a HKUST-1/Cu-TPA hetero structure by synthesizing a Cu-TPA film continuously after the growth of a HKUST-1 film on the CuOx substrate.

  20. Chemoenzymatic Synthesis of Cellular Adhesion Tripeptide RGD Precursor in Organic Media

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    Chemoenzymatic synthesis of tripeptide Bz-RGD-(OEt)2 was conducted in this study. First, the free dipeptide Gly-Asp was synthesized via a novel chemical method, wherein only L-aspartic acid was used and was followed by the esterification of Gly-Asp. The formation of the linkage between the third amino acid Bz-Arg-OEt and Gly-Asp-(OEt)2 was completed by using the enzymatic method in organic media. The effects of several factors such as pH, the water content, triethylamine(TEA), the molar ratio of the substrates, and the reaction time on the yield of Bz-RGD-(OEt)2 were examined. It was obtained that the optimum conditions for Bz-RGD-(OEt)2 synthesis in an ethanol/Tris-HCl buffer system(volume ratio 93:7) were as follows; pH=8.0; temperature, 30 ℃; reaction time, 7 h. The tripeptide yield was 75.2%.

  1. Synthesis and Characterization of an Iron Nitride Constructed by a Novel Template of Metal Organic Framework

    Directory of Open Access Journals (Sweden)

    Suyan Liu

    2015-01-01

    Full Text Available An iron nitride with high surface area was synthesized from an iron-based metal organic framework (Fe-MOF in this work. During the synthesis process, the Fe-MOF of MIL-53 served as a hard template, a template to impart a certain degree of morphology for iron oxide products and to form porosities for iron nitride products. Moreover, it played the roles of iron sources for the synthesis of the final iron oxides and the iron nitrides. The physicochemical properties of the materials were characterized by a series of technologies including XRD, SEM, and N2-adsorption/desorption. The results showed that the iron nitride synthesized from MIL-53 was α-Fe2-3N. And, the α-Fe2-3N showed the morphology with loosely aggregated particles which favored the formation of rich interparticle porosities. As a result, the surface area of the α-Fe2-3N was larger than those of samples using α-Fe2O3 as precursors and its value was 41 m2/g. In addition, the results agreed that both raw material properties (such as crystallinity and surface areas and nitriding approaches had significant effects on the surface areas of iron nitrides. Also the results were proved by the iron oxide synthesized with different methods. This new synthetic strategy could be a general approach for the preparation of late transition metal nitrides with peculiar properties.

  2. An Efficient Synthesis Strategy for Metal-Organic Frameworks: Dry-Gel Synthesis of MOF-74 Framework with High Yield and Improved Performance.

    Science.gov (United States)

    Das, Atanu Kumar; Vemuri, Rama Sesha; Kutnyakov, Igor; McGrail, B Peter; Motkuri, Radha Kishan

    2016-06-16

    Vapor-assisted dry-gel synthesis of the metal-organic framework-74 (MOF-74) structure, specifically Ni-MOF-74 produced from synthetic precursors using an organic-water hybrid solvent system, showed a very high yield (>90% with respect to 2,5-dihydroxyterepthalic acid) and enhanced performance. The Ni-MOF-74 obtained showed improved sorption characteristics towards CO2 and the refrigerant fluorocarbon dichlorodifluoromethane. Unlike conventional synthesis, which takes 72 hours using the tetrahydrofuran-water system, this kinetic study showed that Ni-MOF-74 forms within 12 hours under dry-gel conditions with similar performance characteristics, and exhibits its best performance characteristics even after 24 hours of heating. In the dry-gel conversion method, the physical separation of the solvent and precursor mixture allows for recycling of the solvent. We demonstrated efficient solvent recycling (up to three times) that resulted in significant cost benefits. The scaled-up manufacturing cost of Ni-MOF-74 synthesized via our dry-gel method is 45% of conventional synthesis cost. Thus, for bulk production of the MOFs, the proposed vapor-assisted, dry-gel method is efficient, simple, and inexpensive when compared to the conventional synthesis method.

  3. An Efficient Synthesis Strategy for Metal-Organic Frameworks: Dry-Gel Synthesis of MOF-74 Framework with High Yield and Improved Performance

    Science.gov (United States)

    Das, Atanu Kumar; Vemuri, Rama Sesha; Kutnyakov, Igor; McGrail, B. Peter; Motkuri, Radha Kishan

    2016-06-01

    Vapor-assisted dry-gel synthesis of the metal-organic framework-74 (MOF-74) structure, specifically Ni-MOF-74 produced from synthetic precursors using an organic-water hybrid solvent system, showed a very high yield (>90% with respect to 2,5-dihydroxyterepthalic acid) and enhanced performance. The Ni-MOF-74 obtained showed improved sorption characteristics towards CO2 and the refrigerant fluorocarbon dichlorodifluoromethane. Unlike conventional synthesis, which takes 72 hours using the tetrahydrofuran-water system, this kinetic study showed that Ni-MOF-74 forms within 12 hours under dry-gel conditions with similar performance characteristics, and exhibits its best performance characteristics even after 24 hours of heating. In the dry-gel conversion method, the physical separation of the solvent and precursor mixture allows for recycling of the solvent. We demonstrated efficient solvent recycling (up to three times) that resulted in significant cost benefits. The scaled-up manufacturing cost of Ni-MOF-74 synthesized via our dry-gel method is 45% of conventional synthesis cost. Thus, for bulk production of the MOFs, the proposed vapor-assisted, dry-gel method is efficient, simple, and inexpensive when compared to the conventional synthesis method.

  4. Improved synthesis and hydrogen storage of a microporous metal-organic framework material

    Energy Technology Data Exchange (ETDEWEB)

    Cheng, Shaojuan; Liu, Shaobing [Department of Environmental and Chemical Engineering, Luoyang Institute of Science and Technology, Luoyang, Henan 471023 (China); Zhao, Qiang; Li, Jinping [Research Institute of Special Chemicals, Taiyuan University of Technology, Taiyuan, Shanxi 030024 (China)

    2009-05-15

    A microporous metal-organic framework MOF-5 [Zn{sub 4}O(BDC){sub 3}, BDC 1,4-benzenedicarboxylic] was synthesized with and without H{sub 2}O{sub 2} by improved methods based on the previous studies. The obtained materials were characterized by X-ray diffraction, scanning electron microscopy and nitrogen adsorption, and their hydrogen storage capacities were measured. The synthesis experiments showed that H{sub 2}O{sub 2} favored the growth of high quality sample, large pore volume and high specific surface area. The measurements of hydrogen storage indicated that the sample with higher specific surface area and large pore volume showed better hydrogen storage behavior than other samples. It was suggested that specific surface area and pore volume influenced the capacity of hydrogen storage for MOF-5 material. (author)

  5. Improved synthesis and hydrogen storage of a microporous metal-organic framework material

    Energy Technology Data Exchange (ETDEWEB)

    Cheng Shaojuan [Department of Environmental and Chemical Engineering, Luoyang Institute of Science and Technology, Luoyang, Henan 471023 (China)], E-mail: shaojuanchengwork@hotmail.com; Liu Shaobing [Department of Environmental and Chemical Engineering, Luoyang Institute of Science and Technology, Luoyang, Henan 471023 (China); Zhao Qiang; Li Jinping [Research Institute of Special Chemicals, Taiyuan University of Technology, Taiyuan, Shanxi 030024 (China)

    2009-05-15

    A microporous metal-organic framework MOF-5 [Zn{sub 4}O(BDC){sub 3}, BDC = 1,4-benzenedicarboxylic] was synthesized with and without H{sub 2}O{sub 2} by improved methods based on the previous studies. The obtained materials were characterized by X-ray diffraction, scanning electron microscopy and nitrogen adsorption, and their hydrogen storage capacities were measured. The synthesis experiments showed that H{sub 2}O{sub 2} favored the growth of high quality sample, large pore volume and high specific surface area. The measurements of hydrogen storage indicated that the sample with higher specific surface area and large pore volume showed better hydrogen storage behavior than other samples. It was suggested that specific surface area and pore volume influenced the capacity of hydrogen storage for MOF-5 material.

  6. Mechanoassisted Synthesis of Sulfonated Covalent Organic Frameworks with High Intrinsic Proton Conductivity.

    Science.gov (United States)

    Peng, Yongwu; Xu, Guodong; Hu, Zhigang; Cheng, Youdong; Chi, Chenglong; Yuan, Daqiang; Cheng, Hansong; Zhao, Dan

    2016-07-20

    It is challenging to introduce pendent sulfonic acid groups into modularly built crystalline porous frameworks for intrinsic proton conduction. Herein, we report the mechanoassisted synthesis of two sulfonated covalent organic frameworks (COFs) possessing one-dimensional nanoporous channels decorated with pendent sulfonic acid groups. These COFs exhibit high intrinsic proton conductivity as high as 3.96 × 10(-2) S cm(-1) with long-term stability at ambient temperature and 97% relative humidity (RH). In addition, they were blended with nonconductive polyvinylidene fluoride (PVDF) affording a series of mixed-matrix membranes (MMMs) with proton conductivity up to 1.58 × 10(-2) S cm(-1) and low activation energy of 0.21 eV suggesting the Grotthuss mechanism for proton conduction. Our study has demonstrated the high intrinsic proton conductivity of COFs shedding lights on their wide applications in proton exchange membranes.

  7. Organic phase synthesis of noble metal-zinc chalcogenide core-shell nanostructures.

    Science.gov (United States)

    Kumar, Prashant; Diab, Mahmud; Flomin, Kobi; Rukenstein, Pazit; Mokari, Taleb

    2016-10-15

    Multi-component nanostructures have been attracting tremendous attention due to their ability to form novel materials with unique chemical, optical and physical properties. Development of hybrid nanostructures that are composed of metal-semiconductor components using a simple approach is of interest. Herein, we report a robust and general organic phase synthesis of metal (Au or Ag)-Zinc chalcogenide (ZnS or ZnSe) core-shell nanostructures. This synthetic protocol also enabled the growth of more compositionally complex nanostructures of Au-ZnSxSe1-x alloys and Au-ZnS-ZnSe core-shell-shell. The optical and structural properties of these hybrid nanostructures are also presented.

  8. Accessing Stereochemically Rich Sultams via Microwave-Assisted, Continuous Flow Organic Synthesis (MACOS) Scale-out

    Science.gov (United States)

    Organ, Michael G.; Hanson, Paul R.; Rolfe, Alan; Samarakoon, Thiwanka B.; Ullah, Farman

    2011-01-01

    The generation of stereochemically-rich benzothiaoxazepine-1,1′-dioxides for enrichment of high-throughput screening collections is reported. Utilizing a microwave-assisted, continuous flow organic synthesis platform (MACOS), scale-out of core benzothiaoxazepine-1,1′-dioxide scaffolds has been achieved on multi-gram scale using an epoxide opening/SNAr cyclization protocol. Diversification of these sultam scaffolds was attained via a microwave-assisted intermolecular SNAr reaction with a variety of amines. Overall, a facile, 2-step protocol generated a collection of benzothiaoxazepine-1,1′-dioxides possessing stereochemical complexity in rapid fashion, where all 8 stereoisomers were accessed from commercially available starting materials. PMID:22116791

  9. Synthesis and characterization of tunable coumarin- linked glasses as new class of organic/inorganic phosphors

    Energy Technology Data Exchange (ETDEWEB)

    Luridiana, Alberto; Pretta, Gianluca; Secci, Francesco; Frongia, Angelo [Dipartimento di Scienze Chimiche e Geologiche, Università degli Studi di Cagliari, Complesso universitario di Monserrato, SS 554, bivio per Sestu, Monserrato (Canada) (Italy); Chiriu, Daniele; Carbonaro, Carlo Maria; Corpino, Riccardo [Dipartimento di Fisica, Università degli Studi di Cagliari, Complesso universitario di Monserrato, SS 554, bivio per Sestu, Monserrato (Canada) (Italy); Ricci, Pier Carlo, E-mail: carlo.ricci@dsf.unica.it [Dipartimento di Fisica, Universitá degli Studi di Cagliari, S.P. Monserrato-Sestu Km 0,700, 09042 Monserrato (Canada) (Italy)

    2014-10-21

    It is well known that stilbene with a trans conformation is highly fluorescent. From the viewpoint of molecular structure, coumarins bear a carbon-carbon double bond which is fixed as trans conformation as in trans-stilbene through a lactone structure. This can help to avoid the trans-cis transformation of the double bond under ultraviolet (UV) irradiation as observed in stilbene compounds and results in strong fluorescence and high fluorescence quantum yield and photostability in most of coumarin derivatives. Herein we report some preliminary results about the synthesis and spectroscopic characterization of tunable coumarins and the development of a new linkage protocol for the obtainment of monolayer coumarin-covalently linked glasses. The resulting organic/inorganic coumarin/silica based Self-Assembled Monolayer (SMA) film is proposed as new phosphors for the substituting of critical raw materials, like rare earths, in photonics applications.

  10. Synthesis of 5'-O-DMT-2'-O-TBS Mononucleosides Using an Organic Catalyst.

    Science.gov (United States)

    Lee, Sunggi; Blaisdell, Thomas P; Kasaplar, Pinar; Sun, Xixi; Tan, Kian L

    2014-06-24

    This unit describes a highly effective method to produce 5'-O-DMT-2'-O-TBS mononucleosides selectively using a small organic catalyst. This methodology avoids the tedious protection/deprotection strategy necessary to differentiate the 2'- and 3'-hydroxyl groups in a ribonucleoside. The catalyst was synthesized in two steps, starting from the condensation of valinol and cyclopentyl aldehyde, followed by anionic addition of N-methylimidazole. Ring closure of the amino alcohol with N,N-dimethylformamide dimethyl acetal in methanol furnishes the catalyst. All four 2'-O-TBS protected mono-nucleosides, U, A(Bz), G(Ib), and C(Ac), were produced in a single step using 10 to 20 mol% of the catalyst at room temperature with excellent yields and selectivity. Further transformation to phosphoramidite demonstrates the utility of this protocol in the preparation of monomers useful for automated synthesis of RNA.

  11. Synthesis of copper nanostructures on silica-based particles for antimicrobial organic coatings

    Science.gov (United States)

    Palza, Humberto; Delgado, Katherine; Curotto, Nicolás

    2015-12-01

    Sol-gel based silica nanoparticles of 100 nm were used to interact with copper ions from the dissolution of CuCl2 allowing the synthesis of paratacamite (Cu2(OH)3Cl) nanocrystals of around 20 nm. The method produced well dispersed copper nanostructures directly supported on the surface of the SiO2 particles and was generalized by using a natural zeolite microparticle as support with similar results. These hybrid Cu based nanoparticles released copper ions when immersed in water explaining their antimicrobial behavior against Escherichia coli and Staphylococcus aureus as measured by the minimum inhibitory and minimum bactericidal concentrations (MIC and MBC). Noteworthy, when these nanostructured particles were mixed with an organic coating the resulting film eliminated until a 99% of both bacteria at concentrations as low as 0.01 wt%.

  12. Sonochemical Synthesis of Photoluminescent Nanoscale Eu(III-Containing Metal-Organic Frameworks

    Directory of Open Access Journals (Sweden)

    Cheng-an TAO

    2015-11-01

    Full Text Available Nanoscale lanthanide-containing metal-organic frameworks (MOFs have more and more interest due to their great properties and potential applications, but how to construct them easily is still challenging. Here, we present a facile and rapid synthesis of Eu(III-containing Nanoscale MOF (denoted as NMOF under ultrasonic irradiation. The effect of the ratio and the addition order of metal ions and linkers on the morphology and size of MOFs was investigated. It is found that both of the ratio and the addition order can affect the morphology and size of 1.4-benzenedicarboxylic acid(H2BDC -based MOFs, but they show no evident influence on that of H2aBDC-based MOFs. The former exhibit typical emission bands of Eu(III ions, while the latter only show the photoluminescent properties of ligands.DOI: http://dx.doi.org/10.5755/j01.ms.21.4.9695

  13. Synthesis of Pt3Ni microspheres with high performance for rapid degradation of organic dyes.

    Science.gov (United States)

    Wang, Min; Yang, Yushi; Long, Jia; Mao, Zhou; Qiu, Tong; Wu, Qingzhi; Chen, Xiaohui

    2015-12-01

    In this study, Pt3Ni microspheres consisted of nanoparticles were synthesized without addition of surfactants via the solvothermal route. The obtained sample was characterized by X-ray diffraction (XRD), inductively coupled plasma-atomic emission spectrometer (ICP-AES), X-ray photoelectron spectroscopy (XPS), and field-emission scanning electron microscopy (FESEM). Furthermore, the catalytic performance of as-synthesized Pt3Ni microspheres was evaluated on the degradation of different organic dyes (methylene blue, methyl orange, Congo red, and rhodamine B). The results show that different dyes were rapidly decomposed by Pt3Ni microspheres in different pathways. Among different dyes, the formation and further degradation of the intermediates was observed during the degradation of methylene blue and methyl orange, suggesting the indirect degradation process of these dyes. This study provides not only a promising catalyst for the removal of organic contaminants for environment remediation, but also new insights for Pt3Ni alloy as a high-performance catalyst in organic synthesis.

  14. Synthesis of a Parkinson's Disease Treatment Drug, the "R,R"-Tartrate Salt "of R"-Rasagiline: A Three Week Introductory Organic Chemistry Lab Sequence

    Science.gov (United States)

    Aguilar, Noberto; Garcia, Billy; Cunningham, Mark; David, Samuel

    2016-01-01

    A synthesis of the "R,R"-tartrate salt of the popular anti-Parkinson's drug "R"-rasagiline (Azilect) was adapted to introduce the organic laboratory student to a medically relevant synthesis. It makes use of concepts found in the undergraduate organic chemistry curriculum, appropriately fits into three approximately 4 h lab…

  15. Toward Developing Made-to-Order Metal-Organic Frameworks: Design, Synthesis and Applications

    KAUST Repository

    Ashri, Lubna Y.

    2016-05-26

    Synthesis of materials with certain properties for targeted applications is an ongoing challenge in materials science. One of the most interesting classes of solid-state materials that have been recently introduced with the potential to address this is metal-organic frameworks (MOFs). MOFs chemistry offers a higher degree of control over materials to be synthesized utilizing various new design strategies, such as the molecular building blocks (MBBs) and the supermolecular building layers (SBLs) approaches. Depending on using predetermined building blocks, these strategies permit the synthesis of MOFs with targeted topologies and enable fine tuning of their properties. This study examines a number of aspects of the design and synthesis of MOFs while exploring their possible utilization in two diverse fields related to energy and pharmaceutical applications. Concerning MOFs design and synthesis, the work presented here explores the rational design of various MOFs with predicted topologies and tunable cavities constructed by pillaring pre-targeted 2-periodic SBLs using the ligand-to-axial and six-connected axial-to-axial pillaring strategies. The effect of expanding the confined spaces in prepared MOFs or modifying their functionalities, while preserving the underlying network topology, was investigated. Additionally, The MBBs approach was employed to discover new modular polynuclear rare earth (RE)-MBBs in the presence of different angular polytopic ligands containing carboxylate and nitrogen moieties with the aid of a modulator. The goal was to assess the diverse possible coordination modes and construct highly-connected nets for utility in the design of new MOFs and enhance the predictability of structural outcomes. The effect of adjusting ligands’ length-to-width ratio on the prepared MOFs was also evaluated. As a result, the reaction conditions amenable for reliable formation of the unprecedented octadecanuclear, octanuclear and double tetranuclear RE-MBBs were

  16. Composite polymer/oxide hollow fiber contactors: versatile and scalable flow reactors for heterogeneous catalytic reactions in organic synthesis.

    Science.gov (United States)

    Moschetta, Eric G; Negretti, Solymar; Chepiga, Kathryn M; Brunelli, Nicholas A; Labreche, Ying; Feng, Yan; Rezaei, Fateme; Lively, Ryan P; Koros, William J; Davies, Huw M L; Jones, Christopher W

    2015-05-26

    Flexible composite polymer/oxide hollow fibers are used as flow reactors for heterogeneously catalyzed reactions in organic synthesis. The fiber synthesis allows for a variety of supported catalysts to be embedded in the walls of the fibers, thus leading to a diverse set of reactions that can be catalyzed in flow. Additionally, the fiber synthesis is scalable (e.g. several reactor beds containing many fibers in a module may be used) and thus they could potentially be used for the large-scale production of organic compounds. Incorporating heterogeneous catalysts in the walls of the fibers presents an alternative to a traditional packed-bed reactor and avoids large pressure drops, which is a crucial challenge when employing microreactors.

  17. Development of a Novel, Oxidatively Activated, Safety-Catch Linker for Solid-Phase Asymmetric Organic Synthesis (SPOS)

    Institute of Scientific and Technical Information of China (English)

    LIN,Jun; Hjalmar Skarphedinsson; Stepehen G.Davies

    2004-01-01

    @@ Solid-phase asymmetric organic synthesis has become a very important synthetic strategy within the organic chemistry community.[1] Critical to success in SPOS is a linking strategy which allows both the substrate to be loaded and the product released efficiently from the polymeric support. A safety catch linker[2] (SCL) is in principle a linking molecule orthogonal to the reaction conditions of the library synthesis, which can be easily activated by a simple chemical transformation to allow efficient cleavage of the products from the polymer under mild conditions. In order to introduce the SuperQuat chiral auxiliaries[3] for SOPS, we report herein design and synthesis of a novel safety catch linker for asymmetric conjugate addition reactions.

  18. The Combined C—H Functionalization/Cope Rearrangement: Discovery and Applications in Organic Synthesis

    Science.gov (United States)

    Davies, Huw M. L.; Lian, Yajing

    2012-01-01

    Conspectus The development of methods for the stereoselective functionalization of sp3 C–H bonds is a challenging undertaking. This Account describes the scope of the combined C–H functionalization/Cope rearrangement (CHCR), a reaction that occurs between rhodium-stabilized vinylcarbenoids and substrates containing allylic C–H bonds. Computational studies have shown that the CHCR reaction is initiated by a hydride transfer to the carbenoid from an allyl site of the substrate, which is then rapidly followed by C–C bond formation between the developing rhodium-bound allyl anion and the allyl cation. In principle, the reaction can proceed through four distinct orientations of the vinylcarbenoid and the approaching substrate. The early examples of the CHCR reaction were all highly diastereoselective, consistent with a reaction proceeding via a chair transition state with the vinylcarbenoid adopting an s-cis conformation. Recent computational studies have revealed that other transition state orientations are energetically accessible, and these results have guided the development of highly stereoselective CHCR reactions that proceed through a boat transition state with the vinylcarbenoid in an s-cis configuration. The CHCR reaction has broad applications in organic synthesis. In some new protocols, the CHCR reaction acts as a surrogate to some of the classic synthetic strategies in organic chemistry. The CHCR reaction has served as a synthetic equivalent of the Michael reaction, the vinylogous Mukaiyama aldol reaction, the tandem Claisen rearrangement/Cope rearrangement, and the tandem aldol reaction/siloxy-Cope rearrangement. In all of these cases, the products are generated with very high diastereocontrol. With a chiral dirhodium tetracarboxylate catalyst such as Rh2(S-DOSP)4 or Rh2(S-PTAD)4, researchers can achieve very high levels of asymmetric induction. Applications of the CHCR reaction include the effective enantiodifferentiation of racemic

  19. Organically functionalized mesoporous silica as a support for synthesis and catalysis

    Science.gov (United States)

    McEleney, Kevin Andrew

    class of inorganic-organic hybrid materials. The majority of PMOs prepared utilize simple organic bridges such as ethyl, phenyl or biphenyl. The use of a chiral organic bridging group, such as BINAP, allows the synthesis of chiral PMOs with possible applications in catalysis and separation science. The synthesis of a triethoxysilyl functionalized BINAP as well as its incorporation into PMO materials with 4,4'-bistriethoxysilyl biphenyl or tetraethylorthosilicate as cosilica sources are described.

  20. The Synthesis of 1-Phenyl-1,2,3,4-tetrahydroisoquinolines: An Undergraduate Organic Laboratory Experiment and Class Project.

    Science.gov (United States)

    Letcher, R. M.; Sammes, M. P.

    1985-01-01

    Describes an undergraduate organic chemistry experiment (requiring three/four 3-hour laboratory sessions) involving a four-stage synthesis of 1-phenyl-1,2,3,4-tetrahydroisoquinolines via the Pictet-Spengler route. In addition, the experiment allows students to study the spectra and properties of aklaloid-like materials while completing several…

  1. The Cyclohexanol Cycle and Synthesis of Nylon 6,6: Green Chemistry in the Undergraduate Organic Laboratory

    Science.gov (United States)

    Dintzner, Matthew R.; Kinzie, Charles R.; Pulkrabek, Kimberly; Arena, Anthony F.

    2012-01-01

    A one-term synthesis project that incorporates many of the principles of green chemistry is presented for the undergraduate organic laboratory. In this multistep scheme of reactions, students react, recycle, and ultimately convert cyclohexanol to nylon 6,6. The individual reactions in the project employ environmentally friendly methodologies, and…

  2. Facile synthesis of multiple enzyme-containing metal-organic frameworks in a biomolecule-friendly environment.

    Science.gov (United States)

    Wu, Xiaoling; Ge, Jun; Yang, Cheng; Hou, Miao; Liu, Zheng

    2015-09-01

    The one-step and facile synthesis of multi-enzyme-containing metal-organic framework (MOF) nanocrystals in aqueous solution at 25 °C was reported in this study. The GOx&HRP/ZIF-8 nanocomposite displayed high catalytic efficiency, high selectivity and enhanced stability due to the protecting effect of the framework.

  3. Low Band Gap Polymers for Roll-to-Roll Coated Organic Photovoltaics – Design, Synthesis and Characterization

    DEFF Research Database (Denmark)

    Bundgaard, Eva; Hagemann, Ole; Jørgensen, Mikkel;

    2011-01-01

    In this paper we present the design and synthesis of 25 new low band gap polymers. The polymers were characterized by UV-vis spectroscopy which showed optical band gaps of 2.0–0.9 eV. The polymers which were soluble enough were applied in organic photovoltaics, both small area devices with a spin...

  4. A Model of Problem Solving: Its Operation, Validity, and Usefulness in the Case of Organic-Synthesis Problems.

    Science.gov (United States)

    Tsaparlis, Georgios; Angelopoulous, Vasileios

    2000-01-01

    Presents a test of the limits of the Johnstone--El-Banna model of problem solving as related to students' responses to organic-synthesis problems. Finds that the predicted pattern was observed in both samples, although the model was more useful for students without previous problem-solving training and for field-independent and field-intermediate…

  5. Selenol Protecting Groups in Organic Chemistry: Special Emphasis on Selenocysteine Se-Protection in Solid Phase Peptide Synthesis

    Directory of Open Access Journals (Sweden)

    Stevenson Flemer Jr.

    2011-04-01

    Full Text Available The appearance of selenium in organic synthesis is relatively rare, and thus examples in the literature pertaining to the masking of its considerable reactivity are similarly uncommon. Greene's Protecting Groups in Organic Synthesis, the standard reference for the state of the art in this arena, offers no entries for selenium protective methodology, in stark comparison to its mention of the great variety of protecting groups germane to its chalcogen cousin sulfur. This scarcity of Se-protection methods makes it no less interesting and pertinent toward the construction of selenium-containing organic systems which do indeed require the iterative blocking and de-blocking of selenol functionalities. A selenium-containing system which is especially relevant is selenocysteine, as its use in Solid Phase Peptide Synthesis requires extensive protection of its selenol side chain. This review will attempt to summarize the current state of understanding with regard to selenium protection protocol in organic synthesis. Moreover, it will provide a special emphasis on selenocysteine side chain protection, comprising both the breadth of functionality used for this purpose as well as methods of deprotection.

  6. Microwave-Enhanced Organic Syntheses for the Undergraduate Laboratory: Diels-Alder Cycloaddition, Wittig Reaction, and Williamson Ether Synthesis

    Science.gov (United States)

    Baar, Marsha R.; Falcone, Danielle; Gordon, Christopher

    2010-01-01

    Microwave heating enhanced the rate of three reactions typically performed in our undergraduate organic chemistry laboratory: a Diels-Alder cycloaddition, a Wittig salt formation, and a Williamson ether synthesis. Ninety-minute refluxes were shortened to 10 min using a laboratory-grade microwave oven. In addition, yields improved for the Wittig…

  7. Facile synthesis of one-dimensional organometallic-organic hybrid polymers based on a diphosphorus complex and flexible bipyridyl linkers.

    Science.gov (United States)

    Elsayed Moussa, M; Attenberger, B; Peresypkina, E V; Fleischmann, M; Balázs, G; Scheer, M

    2016-08-21

    The selective synthesis of a series of new "ladderlike" one-dimensional organometallic-organic hybrid polymers is shown. The polymers are obtained from the reaction of the diphosphorus ligand complex [Cp2Mo2(CO)4(η(2)-P2)] with the copper salt [Cu(CH3CN)4]BF4 in the presence of flexible organic bipyridyl linkers in high selectivity. This unique behaviour is supported by DFT calculations.

  8. Abiotic racemization kinetics of amino acids in marine sediments.

    Directory of Open Access Journals (Sweden)

    Andrew D Steen

    Full Text Available The ratios of d- versus l-amino acids can be used to infer the sources and composition of sedimentary organic matter. Such inferences, however, rely on knowing the rates at which amino acids in sedimentary organic matter racemize abiotically between the d- and the l-forms. Based on a heating experiment, we report kinetic parameters for racemization of aspartic acid, glutamic acid, serine, and alanine in bulk sediment from Aarhus Bay, Denmark, taken from the surface, 30 cm, and 340 cm depth below seafloor. Extrapolation to a typical cold deep sea sediment temperature of 3°C suggests racemization rate constants of 0.50×10(-5-11×10(-5 yr(-1. These results can be used in conjunction with measurements of sediment age to predict the ratio of d:l amino acids due solely to abiotic racemization of the source material, deviations from which can indicate the abundance and turnover of active microbial populations.

  9. Synthesis of Nine-atom Deltahedral Zintl Ions of Germanium and their Functionalization with Organic Groups

    Science.gov (United States)

    Gillett-Kunnath, Miriam M.; Sevov, Slavi C.

    2012-01-01

    Although the first studies of Zintl ions date between the late 1890's and early 1930's they were not structurally characterized until many years later.1,2 Their redox chemistry is even younger, just about ten years old, but despite this short history these deltahedral clusters ions E9n- (E = Si, Ge, Sn, Pb; n = 2, 3, 4) have already shown interesting and diverse reactivity and have been at the forefront of rapidly developing and exciting new chemistry.3-6 Notable milestones are the oxidative coupling of Ge94- clusters to oligomers and infinite chains,7-19 their metallation,14-16,20-25 capping by transition-metal organometallic fragments,26-34 insertion of a transition-metal atom at the center of the cluster which is sometimes combined with capping and oligomerization,35-47 addition of main-group organometallic fragments as exo-bonded substituents,48-50 and functionalization with various organic residues by reactions with organic halides and alkynes.51-58 This latter development of attaching organic fragments directly to the clusters has opened up a new field, namely organo-Zintl chemistry, that is potentially fertile for further synthetic explorations, and it is the step-by-step procedure for the synthesis of germanium-divinyl clusters described herein. The initial steps outline the synthesis of an intermetallic precursor of K4Ge9 from which the Ge94- clusters are extracted later in solution. This involves fused-silica glass blowing, arc-welding of niobium containers, and handling of highly air-sensitive materials in a glove box. The air-sensitive K4Ge9 is then dissolved in ethylenediamine in the box and then alkenylated by a reaction with Me3SiC≡CSiMe3. The reaction is followed by electrospray mass spectrometry while the resulting solution is used for obtaining single crystals containing the functionalized clusters [H2C=CH-Ge9-CH=CH2]2-. For this purpose the solution is centrifuged, filtered, and carefully layered with a toluene solution of 18-crown-6. Left

  10. Bulk synthesis of metal-organic hybrid dimers and their propulsion under electric fields.

    Science.gov (United States)

    Wang, Sijia; Ma, Fuduo; Zhao, Hui; Wu, Ning

    2014-03-26

    Metal-organic hybrid particles have great potential in applications such as colloidal assembly, autonomous microrobots, targeted drug delivery, and colloidal emulsifiers. Existing fabrication methods, however, typically suffer from low throughput, high operation cost, and imprecise property control. Here, we report a facile and bulk synthesis platform that makes a wide range of metal-organic colloidal dimers. Both geometric and interfacial anisotropy on the particles can be tuned independently and conveniently, which represents a key advantage of this method. We further investigate the self-propulsion of platinum-polystyrene dimers under perpendicularly applied electric fields. In 1 × 10(-4) M KCl solution, the dimers exhibit both linear and circular motion with the polystyrene lobes facing toward the moving direction, due to the induced-charge electroosmotic flow surrounding the metal-coated lobes. Surprisingly, in deionized water, the same dimers move in an opposite direction, i.e., the metallic lobes face the forward direction. This is because of the impact of another type of electrokinetic flow: the electrohydrodynamic flow arising from the induced charges on the conducting substrate. The competition between the electrohydrodynamic flow along the substrate and the induced-charge electroosmotic flow along the metallic lobe dictates the propulsion direction of hybrid dimers under electric fields. Our synthetic approach will provide potential opportunities to study the combined impacts of the geometric and interfacial anisotropy on the propulsion, assembly, and other applications of anisotropic particles. PMID:24581149

  11. Nanoscaled palladium catalysts on activated carbon support "Sibunit" for fine organic synthesis

    Science.gov (United States)

    Simakova, I.; Koskin, A.; Deliy, I.; Simakov, A.

    2005-08-01

    The application of nanosized palladium catalysts has gained growing importance over the last few years. Palladiumbased catalytic methods for fine organic synthesis permits the replacement of traditional labor-consuming techniques in multi-step organic syntheses and provides an improvement from the standpoint of cost and environmental impact. The use of activated carbon "Sibunit" as a substrate for catalysts has been fostered by the substrate's high surface area, chemical inertness both in acidic and basic media, and at the same time by the absence of very strong acidic centers on its surface which could promote undesirable side reactions during the catalytic run. A conversion of alpha-pinene derivatives to commercial biologically active compounds and fragrances as well as sun screens with ultra violet filtering properties, involves a catalytic hydrogenation as a key intermediate step. The aim of the present work is to clarify the factors favoring the dispersion of Pd metal on carbon. The effect of reduction temperature and pretreatment of the carbon surface on metal size during preparation of Pd on "Sibunit" catalysts for selective verbenol conversion was studied. The electron microscopy method (TEM) was used to show the influence on Pd metal dispersion of carbon surface oxidation by the oxidant H2O2, HNO3. The catalytic activity of Pd/C catalyst samples in verbenol hydrogenation reaction was determined. Kinetic peculiarities of verbenol hydrogenation over the most active catalyst sample were obtained.

  12. A New Energy Source for Organic Synthesis in Europa's Surface Ice

    Science.gov (United States)

    Borucki, Jerome G.; Khare, Bishun; Cruikshank, Dale P.; DeVincenzi, D. (Technical Monitor)

    2002-01-01

    Colored regions on Jupiter's satellite Europa and other icy bodies in the outer Solar System may be contaminated by organic macromolecular solid material that is produced when surface ices are exposed to electrical energy. Hypervelocity meteorite impacts and fracture release tidal and tectonic stresses in icy crusts in the form of electrical discharges, which provide the energy for in situ synthesis of the organic solids. We report measurements of electrical discharge, light emission, and magnetic phenomena in hypervelocity impacts into ice with projectiles with V approx. 5 km/s. Part of the projectile's kinetic energy is converted into electrical potential, while the mechanical disruption of the impact also releases stress energy as light, heat, electrical, and magnetic fields as secondary emissions. These newly recognized energy sources suggest that the dark material in the area of impact craters are tholins generated from the energy of the impacts and that well up from the fracture zone. Large pools of liquid water would persist under the meteorite crater for thousands of years, with the potential for prebiotic chemistry to take place at an accelerated rate due to energy pumped in from the secondary emissions.

  13. Synthesis and studies of novel high metal content organic aerogels obtained from a polymerizable titanium complex

    International Nuclear Information System (INIS)

    Inertial Confinement Fusion (ICF) is a technique widely studied by the French atomic commission (CEA). Experiments will be performed within the Laser Megajoule (LMJ). They require innovative materials like organic aerogels that constitute laser targets. Such polymeric material must provide both a high porosity and a significant titanium percentage (1 atom %). Moreover, the monomers developed must be compatible with the synthesis procedure already in use. According to these specifications, a new polymerizable titanium complex was synthesized and fully characterized. This air and moisture-stable monomer provides a high metal percentage. Its free-radical cross-linked copolymerization affords several titanium-containing polymers. These gels were dried under supercritical conditions and organic aerogels were obtained. The chemical compositions of these materials were investigated by NMR, IR and elemental analysis while their structure was characterized by MEB-EDS, MET, N2 adsorption/desorption isotherms measurements and SAXS. The data collected fit the specification requirements. Moreover, the mechanisms responsible of the foam nano-structure formation were discussed. (author)

  14. Safety aspects of genetically modified crops with abiotic stress tolerance

    NARCIS (Netherlands)

    Liang, C.; Prins, T.W.; Wiel, van de C.C.M.; Kok, E.J.

    2014-01-01

    Abiotic stress, such as drought, salinity, and temperature extremes, significantly reduce crop yields. Hence, development of abiotic stress-tolerant crops by modern biotechnology may contribute to global food security. Prior to introducing genetically modified crops with abiotic stress tolerance to

  15. Functional ecological genomics to demonstrate general and specific responses to abiotic stress

    NARCIS (Netherlands)

    Roelofs, D.; Aarts, M.G.M.; Schat, H.; Straalen, van N.M.

    2008-01-01

    1. Stress is a major component of natural selection in soil ecosystems. The most prominent abiotic stress factors in the field are temperature extremes (heat, cold), dehydration (drought), high salinity and specific toxic compounds such as heavy metals. Organisms are able to deal with these stresses

  16. Effect of abiotic factors on the mercury reduction process by humic acids in aqueous systems

    Science.gov (United States)

    Mercury (Hg) in the environment can have serious toxic effects on a variety of living organisms, and is a pollutant of concern worldwide. The reduction of mercury from the toxic Hg2+ form to Hg0 is especially important. One pathway for this reduction to occur is through an abiotic process with humic...

  17. The effects of bacterial volatile emissions on plant abiotic stress tolerance

    Directory of Open Access Journals (Sweden)

    Xiao-Min eLiu

    2015-09-01

    Full Text Available Plant growth-promoting rhizobacteria (PGPR are beneficial plant symbionts that have been successfully used in agriculture to increase seedling emergence, plant weight, crop yield, and disease resistance. Some PGPR strains release volatile organic compounds (VOCs that can directly and/or indirectly mediate increases in plant biomass, disease resistance, and abiotic stress tolerance. This mini-review focuses on the enhancement of plant abiotic stress tolerance by bacterial VOCs. The review considers how PGPR VOCs induce tolerance to salinity and drought stress and also how they improve sulfur and iron nutrition in plants. The potential complexities in evaluating the effects of PGPR VOCs are also discussed.

  18. An Abiotic Glass-Bead Collector Exhibiting Active Transport

    Science.gov (United States)

    Goto, Youhei; Kanda, Masato; Yamamoto, Daigo; Shioi, Akihisa

    2015-09-01

    Animals relocate objects as needed by active motion. Active transport is ubiquitous in living organisms but has been difficult to realize in abiotic systems. Here we show that a self-propelled droplet can gather scattered beads toward one place on a floor and sweep it clean. This is a biomimetic active transport with loadings and unloadings, because the transport was performed by a carrier and the motion of the carrier was maintained by the energy of the chemical reaction. The oil droplet produced fluctuation of the local number density of the beads on the floor, followed by its autocatalytic growth. This mechanism may inspire the technologies based on active transport wherein chemical and physical substances migrate as in living organisms.

  19. Activity of α-Chymotrypsin Enhanced in the Presence of Iron Oxide Nanoparticles in Organic Solvent: Application to Peptide Synthesis

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Cheolwoo; Kim, Mahnjoo [Pohang Univ. of Science and Technology, Pohang (Korea, Republic of)

    2013-03-15

    We have demonstrated that α-CT displays a significantly enhanced activity in the presence of IONs relative to its IONs-free counterparts in organic solvent. IONs-activated α-CT catalyzed efficiently the synthesis of peptides without the formation of hydrolyzed byproducts. Enzymes are a useful class of catalysts for the preparation of enantiomeric compounds. The applications of enzymes in synthetic transformations, however, are limited by their reduced activities in organic solvent. Particularly, proteases such as subtilisin and α-chymotrypsin display several orders of magnitude lower activities in organic solvent than their aqueous counterparts.

  20. Baylis-Hillman acetates in organic synthesis: convenient one-pot synthesis of α-carboline framework--a concise synthesis of neocryptolepine.

    Science.gov (United States)

    Basavaiah, Deevi; Mallikarjuna Reddy, Daggula

    2012-11-28

    A convenient, facile, and one-pot methodology for the synthesis of α-carbolines from Baylis-Hillman (BH) acetates, involving three steps (reactions), (1) mono alkylation of 2-nitroarylacetonitriles with BH-acetates, (2) reduction of nitro group into amino group using Fe/AcOH and (3) formation of two (five and six membered) rings, is presented. This methodology is successfully applied to the synthesis of bioactive alkaloid neocryptolepine.

  1. The first one-pot synthesis of metal-organic frameworks functionalised with two transition-metal complexes.

    Science.gov (United States)

    Platero-Prats, Ana E; Bermejo Gómez, Antonio; Samain, Louise; Zou, Xiaodong; Martín-Matute, Belén

    2015-01-01

    The synthesis of a metal-organic framework (UiO-67) functionalised simultaneously with two different transition metal complexes (Ir and Pd or Rh) through a one-pot procedure is reported for the first time. This has been achieved by an iterative modification of the synthesis parameters combined with characterisation of the resulting materials using different techniques, including X-ray absorption spectroscopy (XAS). The method also allows the first synthesis of UiO-67 with a very wide range of loadings (from 4 to 43 mol %) of an iridium complex ([IrCp*(bpydc)(Cl)Cl](2-) ; bpydc=2,2'-bipyridine-5,5'-dicarboxylate, Cp*=pentamethylcyclopentadienyl) through a pre-functionalisation methodology.

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

    Science.gov (United States)

    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.

  3. Highly efficient synthesis of endomorphin-2 under thermodynamic control catalyzed by organic solvent stable proteases with in situ product removal.

    Science.gov (United States)

    Xu, Jiaxing; Sun, Honglin; He, Xuejun; Bai, Zhongzhong; He, Bingfang

    2013-02-01

    An efficient enzymatic synthesis of endomorphin-2 (EM-2) was achieved using organic solvent stable proteases in nonaqeous media, based on thermodynamic control and an in situ product removal methodology. The high stability of biocatalysts in organic solvents enabled the aleatoric modulation of the nonaqueous reaction media to shift thermodynamic equilibrium toward synthesis. Peptide Boc-Phe-Phe-NH2 was synthesized with a high yield of 96% by the solvent stable protease WQ9-2 in monophase medium with an economical molar ratio of the substrate of 1:1. The tetrapeptide Boc-Tyr-Pro-Phe-Phe-NH2 was synthesized with a yield of 88% by another organic solvent tolerant protease PT121 from Boc-Tyr-Pro-OH and Phe-Phe-NH2 in an organic-aqueous biphasic system. The reaction-separation coupling in both enzymatic processes provides "driving forces" for the synthetic reactions and gives a high yield and high productivity without purification of the intermediate, thereby making the synthesis more amenable to scale-up. PMID:23305895

  4. Highly efficient synthesis of endomorphin-2 under thermodynamic control catalyzed by organic solvent stable proteases with in situ product removal.

    Science.gov (United States)

    Xu, Jiaxing; Sun, Honglin; He, Xuejun; Bai, Zhongzhong; He, Bingfang

    2013-02-01

    An efficient enzymatic synthesis of endomorphin-2 (EM-2) was achieved using organic solvent stable proteases in nonaqeous media, based on thermodynamic control and an in situ product removal methodology. The high stability of biocatalysts in organic solvents enabled the aleatoric modulation of the nonaqueous reaction media to shift thermodynamic equilibrium toward synthesis. Peptide Boc-Phe-Phe-NH2 was synthesized with a high yield of 96% by the solvent stable protease WQ9-2 in monophase medium with an economical molar ratio of the substrate of 1:1. The tetrapeptide Boc-Tyr-Pro-Phe-Phe-NH2 was synthesized with a yield of 88% by another organic solvent tolerant protease PT121 from Boc-Tyr-Pro-OH and Phe-Phe-NH2 in an organic-aqueous biphasic system. The reaction-separation coupling in both enzymatic processes provides "driving forces" for the synthetic reactions and gives a high yield and high productivity without purification of the intermediate, thereby making the synthesis more amenable to scale-up.

  5. Abiotic stress tolerance and competition-related traits underlie phylogenetic clustering in soil bacterial communities.

    Science.gov (United States)

    Goberna, Marta; Navarro-Cano, Jose A; Valiente-Banuet, Alfonso; García, Carlos; Verdú, Miguel

    2014-10-01

    Soil bacteria typically coexist with close relatives generating widespread phylogenetic clustering. This has been ascribed to the abiotic filtering of organisms with shared ecological tolerances. Recent theoretical developments suggest that competition can also explain the phylogenetic similarity of coexisting organisms by excluding large low-competitive clades. We propose that combining the environmental patterns of traits associated with abiotic stress tolerances or competitive abilities with phylogeny and abundance data, can help discern between abiotic and biotic mechanisms underlying the coexistence of phylogenetically related bacteria. We applied this framework in a model system composed of interspersed habitats of highly contrasted productivity and comparatively dominated by biotic and abiotic processes, i.e. the plant patch-gap mosaic typical of drylands. We examined the distribution of 15 traits and 3290 bacterial taxa in 28 plots. Communities showed a marked functional response to the environment. Conserved traits related to environmental stress tolerance (e.g. desiccation, formation of resistant structures) were differentially selected in either habitat, while competition related traits (e.g. organic C consumption, formation of nutrient-scavenging structures) prevailed under high resource availability. Phylogenetic clustering was stronger in habitats dominated by biotic filtering, suggesting that competitive exclusion of large clades might underlie the ecological similarity of co-occurring soil bacteria.

  6. Organic Synthesis and Potential Microbiology in the Solar Nebula: Are Early Solar Systems Nurseries for Microorganisms?

    Science.gov (United States)

    Mautner, M. N.; Ibrahim, Y.; El-Shall, M. S.

    2004-11-01

    We observed a new synthetic mechanism that can contribute organics toward the origins of life in the solar nebula. We also observed that microorganisms can grow on carbonaceous asteroid/meteorite materials, suggesting that micoorganisms can multiply in aqueous asteroids in the early Solar System. The new synthetic mechanism is provided by ionized polycyclic aromatic hydrocarbons in cold nebular and interstellar cloud environments, through associative charge transfer (ACT) and associative proton transfer (APT) reactions. For example, ionized benzene (C6H6+) reacts with two CH3CH=CH2 molecules to form C6H12+ that initiates ionic polymerization. Other unsaturated molecules (HCCH, H2CO, HCN, CH3CN) can yield complex organics by this mechanism. The C6H6+ ion also reacts with water molecules to form (H2O)nH+ nucleation centers for ices, in which UV-induced organic synthesis can occur. The organics in the nebula can contribute to the origins of life and support microorganisms. For example, we observed that microorganisms such as Nocardia asteroides, algae, fungi, and even plant cultures (Asparagus officinalis) grow in planetary microcosms based on carbonaceous chondrite, as well as Martian, meteorites. We found high microbial populations (10exp7 CFU/ml) and complex microbial communities in these planetary microcosms. Thermophilic archaebacteria also grew on these materials. The results suggest that early aqueous asteroids can support microorganisms, distribute them through the solar nebula by collisions, deliver them to planets, and possibly eject them to interstellar space. Such natural panspermia processes, or directed panspermia payloads, may seed other young solar systems where microbial life can multiply by similar mechanisms. We thank NASA Grant NNG04GH45G for funding support. References: 1. M. N. Mautner, Planetary Bioresources and Astroecology...., Icarus 2002, 158, 72-86; see www.astroecology.com. 2. M. Mautner and G. L. Matloff, Directed Panspermia...., Bull

  7. Study of the Performance of the Organic Extracts of Chenopodium ambrosioides for Ag Nanoparticle Synthesis

    Directory of Open Access Journals (Sweden)

    Luis M. Carrillo-López

    2016-01-01

    Full Text Available There are many ways to obtain metal nanoparticles: biological, physical, and chemical ways and combinations of these approaches. Synthesis assisted with plant extracts has been widely documented. However, one issue that is under discussion refers to the metabolites responsible for reduction and stabilization that confine nanoparticle growth and prevent coalescence between nanoparticles in order to avoid agglomeration/precipitation. In this study, Ag nanoparticles were synthesized using organic extracts of Chenopodium ambrosioides with different polarities (hexane, dichloromethane, and methanol. Each extract was phytochemically characterized to identify the nature of the metabolites responsible for nanoparticle formation. With methanol extract, the compounds responsible for reducing and stabilizing silver nanoparticle were associated with the presence of phenolic compounds (flavonoids and tannins, while, with dichloromethane and hexane extracts, the responsible compounds were mainly terpenoids. Large part of the reducing activity of secondary metabolites in C. ambrosioides is closely related to compounds with antioxidant capacity, such as phenolic compounds (flavone glycoside and isorhamnetin, which are the main constituents of the methanol extracts. Otherwise, terpenoids (trans-diol, α-terpineol, monoterpene hydroperoxides, and apiole are the central metabolites present in dichloromethane and hexane extracts.

  8. Progammed synthesis of magnetic mesoporous silica coated carbon nanotubes for organic pollutant adsorption

    Science.gov (United States)

    Tong, Yue; Zhang, Min; Xia, Peixiong; Wang, Linlin; Zheng, Jing; Li, Weizhen; Xu, Jingli

    2016-05-01

    Magnetic mesoporous silica coated carbon nanotubes were produced from hydrophilic monodisperse magnetic nanoparticles decorated carbon nanotubes using well controlled programmed synthesis method and were characterized by TEM, XRD, FTIR, TGA, N2 adsorption-desorption and VSM. The well-designed mesoporous magnetic nanotubes had a large specific area, a highly open mesoporous structure and high magnetization. Firstly, SiO2-coated maghemite/CNTs nanoparticles (CNTs/Fe3O4@SiO2 composites) were synthesized by the combination of high temperature decomposition process and an sol-gel method, in which the iron acetylacetonate as well as TEOS acted as the precursor for maghemite and SiO2, respectively. The CNTs/Fe3O4@SiO2 composites revealed a core-shell structure, Then, CNTs/Fe3O4@mSiO2 was obtained by extracting cetyltrimethylammonium bromide (CTAB) via an ion-exchange procedure. The resulting composites show not only a magnetic response to an externally applied magnetic field, but also can be a good adsorbent for the organic pollutant in the ambient temperature.

  9. A study on metal organic framework (MOF-177) synthesis, characterization and hydrogen adsorption -desorption cycles

    Energy Technology Data Exchange (ETDEWEB)

    Viditha, V.; Venkateswer Rao, M.; Srilatha, K.; Himabindu, V. [Centre for Environment, Institute of Science and Technology, Jawaharlal Nehru Technological University Hyderabad, Kukatpally, Hyderabad-500 085, A.P. (India); Yerramilli, Anjaneyulu [Director, TLGVRC, JSU Box 18739, JSU, Jackson, MS 32917-0939 (United States)

    2013-07-01

    Hydrogen has long been considered to be an ideal alternative to fossil-fuel systems and much work has now been done on its storage. There are four main methods of hydrogen storage: as a liquid; as compressed hydrogen; in the form of metal hydrides; and by physisorption. Among all the materials metal organic frameworks (MOFs) are considered to have desirable properties like high porosity, pore volume and high thermal stability. MOF-177 is considered to be an ideal storage material. In this paper we study about its synthesis and hydrogen storage capacities of MOF-177 at different pressures ranging from 25, 50, 75 and 100 bar respectively. The obtained samples are characterized by XRD, BET and SEM. The recorded results show that the obtained hydrogen capacity is 1.1, 2.20, 2.4 and 2.80 wt%. The desorption capacity is 0.9, 2.1, 2.37 and 2.7 wt% at certain temperatures like 373 K.

  10. Preparation of fluorescent DNA probe by solid-phase organic synthesis

    Directory of Open Access Journals (Sweden)

    2009-08-01

    Full Text Available Fluorescent DNA probe based on fluorescence resonance energy transfer (FRET was prepared by solid-phase organic synthesis when CdTe quantum dots (QDs were as energy donors and Au nanoparticles (AuNPs were as energy accepters. The poly(divinylbenzene core/poly(4-vinylpyridine shell microspheres, as solid-phase carriers, were prepared by seeds distillation-precipitation polymerization with 2,2′-azobisisobutyronitrile (AIBN as initiator in neat acetonitrile. The CdTe QDs and AuNPs were self-assembled on the surface of core/shell microspheres, and then the linkage of CdTe QDs with oligonucleotides (CdTe-DNA and AuNPs with complementary single-stranded DNA (Au-DNA was on the solid-phase carriers instead of in aqueous solution. The hybridization of complementary double stranded DNA (dsDNA bonded to the QDs and AuNPs (CdTe-dsDNA-Au determined the FRET distance of CdTe QDs and AuNPs. Compared with the fluorescence of CdTe-DNA, the fluorescence of CdTe-dsDNA-Au conjugates (DNA probes decreased extremely, which indicated that the FRET occurred between CdTe QDs and AuNPs. The probe system would have a certain degree recovery of fluorescence when the complementary single stranded DNA was introduced into this system, which showed that the distance between CdTe QDs and AuNPs was increased.

  11. Synthesis and fluorescent properties of poly(arylpyrazoline)'s for organic-electronics

    Science.gov (United States)

    Vandana, T.; Ramkumar, V.; Kannan, P.

    2016-08-01

    The present work focuses on the synthesis and characterization of poly(arylchalcone)'s (PCH I-IV) by reacting acetone with various dialdehydes for the first time at below ambient temperature followed by cyclization with phenylhydrazinehydrochloride to yield luminescent poly(arylpyrazoline)'s (PPY I-IV). The synthesized polymers were characterized by standard techniques such as, GPC, SEM, TGA, FT-IR, 1H NMR, UV-Vis absorption and fluorescence spectroscopy, and electrochemical studies by cyclic voltammetry analyses. The Pyrazoline group hooked with different aryl donors such as benzene, thiophene, carbazole, triphenylamine, thus results a series of blue and green emitting materials. The obtained optical bandgap energy of the polymers (PPY I-IV) were 2.53, 3.41, 3.07, 3.10 eV respectively, suggest that all the polymers belongs to semiconducting category. The solvent effect of polymers was thoroughly studied and explained by Lippert-Mataga equation. The polymers I & IV display large degree of intra-molecular charge transfer in excited state evidenced from solvatochromic shift on the emission spectra. The obtained results demonstrate that they are promising materials for organic electronics applications.

  12. Epidermal DNA synthesis in organ culture explants. A study of hairless mouse ear epidermis.

    Science.gov (United States)

    Hansteen, I L; Iversen, O H; Refsum, S B

    1979-10-01

    Explants of split mouse ear were incubated in organ culture for up to 48 h, and the cell proliferation was studied by the addition of Thymidine-methyl-3-H (3HTdR) to the medium during different time periods, mainly for the first 14 h of incubation. Cultures were started at 0900, 2130 and 2300. In all cases the labelling index remained stable for 6-8 h, and then increased. The mean grain count, however, was falling and so was the epidermal DNA-specific uptake of 3HTdR. Based on the experimental results, calculations can be made of the flux of cells through S. It is concluded that the increasing LI is not due to inherent diurnal variation in cell proliferation, and is not a sign of real growth but caused instead by a complete block of the cell exit from S, probably combined with periods of an increased entrance rate into S. Other methodological factors, however, may also contribute to the increasing LI. Hence, this system is not suited for the measurement of factors that influence epidermal DNA synthesis.

  13. Engymatic synthesis of aspartame precursor in organic solvent; Yuki yobaichu deno asuparutemu zenkutai no koso gosei

    Energy Technology Data Exchange (ETDEWEB)

    Nakanishi, K. [Okayama Univ., Okayama (Japan). Faculty of Engineering

    1996-11-05

    Taking up the synthetic reaction of the precursor of artificial sweetener aspartame for which thermolysin is used as the catalyst, the features and problems of enzymatic reaction in organic solvent are discussed. It is found that immobilized enzyme which has high activity and stability can be prepared by adsorbing high concentration thermolysin in Amberlite XAD7 followed by bridge immobilization. The initial rate of the synthesis and the stability of immobilized enzyme depend on the types of solvents. Continuous reaction is attempted using a columnar ferment reactor (PFR) in ethyl acetate at the beginning, but the yield decreases in a short period because the immobilized enzyme lose its activity gradually from the upper area of the column where Z-Asp concentration is high. When CSTR (complete mixed type reactor) is used, deactivation of immobilized enzyme can be restricted because low Z-Asp concentration in the reactor can be maintained. It is demonstrated that continuous reaction of longer than 200 hours is possible although the reaction rate is as low as 90%. 4 refs., 3 figs., 1 tab.

  14. A study on metal organic framework (MOF-177 synthesis, characterization and hydrogen adsorption -desorption cycles

    Directory of Open Access Journals (Sweden)

    V.Viditha, M.Venkateswer Rao, K.Srilatha11, V.Himabindu, Anjaneyulu Yerramilli

    2013-01-01

    Full Text Available Hydrogen has long been considered to be an ideal alternative to fossil-fuel systems and much work has now been done on its storage. There are four main methods of hydrogen storage: as a liquid; as compressed hydrogen; in the form of metal hydrides; and by physisorption. Among all the materials metal organic frameworks (MOFs are considered to have desirable properties like high porosity, pore volume and high thermal stability. MOF-177 is considered to be an ideal storage material. In this paper we study about its synthesis and hydrogen storage capacities of MOF-177 at different pressures ranging from 25, 50, 75 and 100 bar respectively. The obtained samples are characterized by XRD, BET and SEM. The recorded results show that the obtained hydrogen capacity is 1.1, 2.20, 2.4 and 2.80 wt%. The desorption capacity is 0.9, 2.1, 2.37 and 2.7 wt% at certain temperatures like 373 K.

  15. Synthesis, characterization, and applications of electroactive polymeric nanostructures for organic coatings

    Science.gov (United States)

    Suryawanshi, Abhijit Jagnnath

    Electroactive polymers (EAP) such as polypyrrole (PPy) and polyaniline (PANI) are being explored intensively in the scientific community. Nanostructures of EAPs have low dimensions and high surface area enabling them to be considered for various useful applications. These applications are in several fields including corrosion inhibition, capacitors, artificial muscles, solar cells, polymer light emitting diodes, and energy storage devices. Nanostructures of EAPs have been synthesized in different morphologies such as nanowires, nanorods, nanotubes, nanospheres, and nanocapsules. This variety in morphology is traditionally achieved using soft templates, such as surfactant micelles, or hard templates, such as anodized aluminum oxide (AAO). Templates provide stability and groundwork from which the polymer can grow, but the templates add undesirable expense to the process and can change the properties of the nanoparticles by integrating its own properties. In this study a template free method is introduced to synthesize EAP nanostructures of PPy and PANI utilizing ozone oxidation. The simple techniques involve ozone exposure to the monomer solution to produce aqueous dispersions of EAP nanostructures. The synthesized nanostructures exhibit uniform morphology, low particle size distribution, and stability against agglomeration. Ozone oxidation is further explored for the synthesis of silver-PPy (Ag-PPy) core-shell nanospheres (CSNs). Coatings containing PPy nanospheres were formulated to study the corrosion inhibition efficiency of PPy nanospheres. Investigation of the coatings using electrochemical techniques revealed that the PPy nanospheres may provide corrosion inhibition against filiform corrosion by oxygen scavenging mechanism. Finally, organic corrosion inhibitors were incorporated in PPy to develop efficient corrosion inhibiting systems, by using the synergistic effects from PPy and organic corrosion inhibitors.

  16. An in situ study of resin-assisted solvothermal metal-organic framework synthesis

    Science.gov (United States)

    Moorhouse, Saul J.; Wu, Yue; O'Hare, Dermot

    2016-04-01

    A newly developed in situ monochromatic high-energy X-ray diffraction setup was used to investigate the synthesis of MOFs using cation-impregnated polymer resin beads as a ion source. The Co-NDC-DMF (NDC=2,6-naphthalenedicarboxylate; DMF=dimethylformamide) system was investigated, a system which is known to produce at least three distinct frameworks. It was found that the resin-assisted synthesis results in the preferential formation of a topology previously impossible to synthesise in bulk, while the comparable nitrate-salt synthesis appeared to form an alternative phases. It was also found that the resin-assisted synthesis is highly diffusion-controlled.

  17. Self-organization of the Sound Inventories: Analysis and Synthesis of the Occurrence and Co-occurrence Networks of Consonants

    CERN Document Server

    Mukherjee, A; Choudhury, M; Ganguly, N; Basu, Anupam; Choudhury, Monojit; Ganguly, Niloy; Mukherjee, Animesh

    2006-01-01

    The sound inventories of the world's languages self-organize themselves giving rise to similar cross-linguistic patterns. In this work we attempt to capture this phenomenon of self-organization, which shapes the structure of the consonant inventories, through a complex network approach. For this purpose we define the occurrence and co-occurrence networks of consonants and systematically study some of their important topological properties. A crucial observation is that the occurrence as well as the co-occurrence of consonants across languages follow a power law distribution. This property is arguably a consequence of the principle of preferential attachment. In order to support this argument we propose a synthesis model which reproduces the degree distribution for the networks to a close approximation. We further observe that the co-occurrence network of consonants show a high degree of clustering and subsequently refine our synthesis model in order to incorporate this property. Finally, we discuss how prefer...

  18. Hydrothermal Synthesis and Characterization of a Metal-Organic Framework by Thermogravimetric Analysis, Powder X-Ray Diffraction, and Infrared Spectroscopy: An Integrative Inorganic Chemistry Experiment

    Science.gov (United States)

    Crane, Johanna L.; Anderson, Kelly E.; Conway, Samantha G.

    2015-01-01

    This advanced undergraduate laboratory experiment involves the synthesis and characterization of a metal-organic framework with microporous channels that are held intact via hydrogen bonding of the coordinated water molecules. The hydrothermal synthesis of Co[subscript 3](BTC)[subscript 2]·12H[subscript 2]O (BTC = 1,3,5-benzene tricarboxylic acid)…

  19. Novel Easy Preparations of Some Aromatic Iodine(I, III, and V) Reagents, Widely Applied in Modern Organic Synthesis

    OpenAIRE

    Lech Skulski

    2003-01-01

    We report our novel (or considerably improved) methods for the synthesis of aromatic iodides, (dichloroiodo)arenes, (diacetoxyiodo)arenes, [bis(trifluoroacetoxy)-iodo]arenes, iodylarenes and diaryliodonium salts, as well as some facile, oxidative anion metatheses in crude diaryliodonium or tetraalkylammonium halides and, for comparison, potassium halides. All our formerly published papers were discussed and explained in our review “Organic Iodine(I, III, and V) Chemistry: 10 Years of Dev...

  20. Microwave-assisted modulated synthesis of zirconium-based metal-organic framework (Zr-MOF) for hydrogen storage applications

    Energy Technology Data Exchange (ETDEWEB)

    Ren, Jianwei; Segakweng, Tshiamo; Langmi, Henrietta W.; Musyoka, Nicholas M.; North, Brian C.; Mathe, Mkhulu [Council for Scientific and Industrial Research (CSIR), Pretoria (South Africa). HySA Infrastructure Centre of Competence, Materials Science and Manufacturing; Bessarabov, Dmitri [North-West Univ. (NWU), Potchefstroom (South Africa). HySA Infrastructure Centre of Competence

    2014-05-15

    Zirconium-based metal-organic framework (Zr-MOF) was synthesized using a microwave-assisted modulated method in a short reaction time of 5 min. The Zr-MOF material was highly crystalline with well-defined octahedral shaped crystals, and it exhibited comparable hydrogen storage capacity to Zr-MOF of similar specific surface area synthesized using conventional methods with much longer synthesis time. (orig.)

  1. Selecting optimal conditions for Alcalase CLEA-OM for synthesis of dipeptides in organic media

    NARCIS (Netherlands)

    Vossenberg, P.; Beeftink, H.H.; Nuijens, T.; Cohen Stuart, M.A.; Tramper, J.

    2012-01-01

    In protease-catalyzed peptide synthesis, the availability of water is essential, as a compromise must be made between on the one hand the overall enzymatic activity and, on the other hand, the rate of product synthesis. Water is essential for enzyme activity, but at the same time causes hydrolytic s

  2. A Safer and Convenient Synthesis of Sulfathiazole for Undergraduate Organic and Medicinal Chemistry Classes

    Science.gov (United States)

    Boyle, Jeff; Otty, Sandra; Sarojini, Vijayalekshmi

    2012-01-01

    A safer method for the synthesis of the sulfonamide drug sulfathiazole, for undergraduate classes, is described. This method improves upon procedures currently followed in several undergraduate teaching laboratories for the synthesis of sulfathiazole. Key features of this procedure include the total exclusion of pyridine, which has potential…

  3. Synthesis of 5,5-Diphenyl-4-penten-2-One: A Variation on a Classic Organic Synthesis Laboratory

    Science.gov (United States)

    Alber, Joshua P.; DeGrand, Michael J.; Cermak, Diana M.

    2011-01-01

    The Grignard reaction and the addition of protecting groups are standard reactions in an organic chemistry course. Organic students learn about the "quench" step of the Grignard reaction using acid and water and the acid-catalyzed hydrolysis to remove the protecting group, yet in the lecture students find these two reactions to be confusing in…

  4. Unveiling the Redox Control of Plant Reproductive Development during Abiotic Stress

    Science.gov (United States)

    Zinta, Gaurav; Khan, Asif; AbdElgawad, Hamada; Verma, Vipasha; Srivastava, Ashish Kumar

    2016-01-01

    Plants being sessile in nature are often challenged to various abiotic stresses including temperature fluctuations, water supply, salinity, and nutrient availability. Exposure of plants to such environmental perturbations result in the formation of reactive oxygen species (ROS) in cells. To scavenge ROS, enzymatic and molecular antioxidants are produced at a cellular level. ROS act as a signaling entity at lower concentrations maintaining normal growth and development, but if their levels increase beyond certain threshold, they produce toxic effects in plants. Some developmental stages, such as development of reproductive organs are more sensitive to abiotic stress than other stages of growth. As success of plant reproductive development is directly correlated with grain yield, stresses coinciding with reproductive phase results in the higher yield losses. In this article, we summarize the redox control of plant reproductive development, and elaborate how redox homeostasis is compromised during abiotic stress exposure. We highlight why more emphasis should be given to understand redox control of plant reproductive organ development during abiotic stress exposure96to engineer crops with better crop yield. We specifically discuss the role of ROS as a signaling molecule and its cross-talk with other signaling molecules such as hormones and sugars. PMID:27379102

  5. One-step synthesis of hybrid inorganic-organic nanocomposite coatings by novel laser adaptive ablation deposition technique

    Science.gov (United States)

    Serbezov, Valery; Sotirov, Sotir

    2013-03-01

    A novel approach for one-step synthesis of hybrid inorganic-organic nanocomposite coatings by new modification of Pulsed Laser Deposition technology called Laser Adaptive Ablation Deposition (LAAD) is presented. Hybrid nanocomposite coatings including Mg- Rapamycin and Mg- Desoximetasone were produced by UV TEA N2 laser under low vacuum (0.1 Pa) and room temperature onto substrates from SS 316L, KCl and NaCl. The laser fluence for Mg alloy was 1, 8 J/cm2 and for Desoximetasone 0,176 J/cm2 and for Rapamycin 0,118 J/cm2 were respectively. The threedimensional two-segmented single target was used to adapt the interaction of focused laser beam with inorganic and organic material. Magnesium alloy nanoparticles with sizes from 50 nm to 250 nm were obtained in organic matrices. The morphology of nanocomposites films were studied by Bright field / Fluorescence optical microscope and Scanning Electron Microscope (SEM). Fourier Transform Infrared (FTIR) spectroscopy measurements were applied in order to study the functional properties of organic component before and after the LAAD process. Energy Dispersive X-ray Spectroscopy (EDX) was used for identification of Mg alloy presence in hybrid nanocomposites coatings. The precise control of process parameters and particularly of the laser fluence adjustment enables transfer on materials with different physical chemical properties and one-step synthesis of complex inorganic- organic nanocomposites coatings.

  6. Synthesis of Isopropyl Ferulate Using Silica-Immobilized Lipase in an Organic Medium

    Science.gov (United States)

    Kumar, Ashok; Kanwar, Shamsher Singh

    2011-01-01

    Immobilization of lipases has proved to be a useful technique for improving an enzyme's activity in organic solvents. In the present study, the performance of a silica-immobilized lipase was evaluated for the synthesis of isopropyl ferulate in DMSO. The biocatalyst was cross-linked onto the matrix with 1% glutaraldehyde. The effects of various parameters, molar ratio of ferulic acid to isopropyl alcohol (25 mM : 100 mM), concentration of biocatalyst (2.5–20 mg/mL), molecular sieves (25–250 mg/mL), and various salt ions, were studied consecutively as a function of percent esterification. Immobilized lipase at 25 mg/mL showed maximum esterification (~84%) of ferulic acid and isopropanol at a molar ratio of 25 mM : 100 mM, respectively, in DMSO at 45°C in 3 h under shaking (150 rpm). To overcome the inhibitory effect of water (a byproduct) if any, in the reaction mixture, molecular sieves (3 Å × 1.5 mm; 100 mg/mL) were added to the reaction mixture to promote the forward reaction. Salt ions like Ca2+, Cd2+, and Fe2+ enhanced the activity of immobilized biocatalyst while a few ions like Co2+, Zn2+, Mg2+, Mn2+, Al3+, and Na+ had mild inhibitory effect. Approximately, one third of total decrease in the esterification efficacy was observed after the 5th repetitive cycle of esterification. PMID:21603272

  7. Synthesis and gas adsorption study of porous metal-organic framework materials

    Science.gov (United States)

    Mu, Bin

    Metal-organic frameworks (MOFs) or porous coordination polymers (PCPs) have become the focus of intense study over the past decade due to their potential for advancing a variety of applications including air purification, gas storage, adsorption separations, catalysis, gas sensing, drug delivery, and so on. These materials have some distinct advantages over traditional porous materials such as the well-defined structures, uniform pore sizes, chemically functionalized sorption sites, and potential for postsynthetic modification, etc. Thus, synthesis and adsorption studies of porous MOFs have increased substantially in recent years. Among various prospective applications, air purification is one of the most immediate concerns, which has urgent requirements to improve current nuclear, biological, and chemical (NBC) filters involving commercial and military purposes. Thus, the major goal of this funded project is to search, synthesize, and test these novel hybrid porous materials for adsorptive removal of toxic industrial chemicals (TICs) and chemical warfare agents (CWAs), and to install the benchmark for new-generation NBC filters. The objective of this study is three-fold: (i) Advance our understanding of coordination chemistry by synthesizing novel MOFs and characterizing these porous coordination polymers; (ii) Evaluate porous MOF materials for gasadsorption applications including CO2 capture, CH4 storage, other light gas adsorption and separations, and examine the chemical and physical properties of these solid adsorbents including thermal stability and heat capacity of MOFs; (iii) Evaluate porous MOF materials for next-generation NBC filter media by adsorption breakthrough measurements of TICs on MOFs, and advance our understanding about structureproperty relationships of these novel adsorbents.

  8. Metal-Organic Frameworks: Building Block Design Strategies for the Synthesis of MOFs.

    KAUST Repository

    Luebke, Ryan

    2014-09-01

    A significant and ongoing challenge in materials chemistry and furthermore solid state chemistry is to design materials with the desired properties and characteristics. The field of Metal-Organic Frameworks (MOFs) offers several strategies to address this challenge and has proven fruitful at allowing some degree of control over the resultant materials synthesized. Several methodologies for synthesis of MOFs have been developed which rely on use of predetermined building blocks. The work presented herein is focused on the utilization of two of these design principles, namely the use of molecular building blocks (MBBs) and supermolecular building blocks (SBBs) to target MOF materials having desired connectivities (topologies). These design strategies also permit the introduction of specific chemical moieties, allowing for modification of the MOFs properties. This research is predominantly focused on two platforms (rht-MOFs and ftw-MOFs) which topologically speaking are edge transitive binodal nets; ftw being a (4,12)-connected net and rht being a (3,24)-connected net. These highly connected nets (at least one node having connectivity greater than eight) have been purposefully targeted to increase the predictability of structural outcome. A general trend in topology is that there is an inverse relationship between the connectivity of the node(s) and the number of topological outcomes. Therefore the key to this research (and to effective use of the SBB and MBB approaches) is identification of conditions which allow for reliable formation of the targeted MBBs and SBBs. In the case of the research presented herein: a 12-connected Group IV or Rare Earth based hexanuclear MBB and a 24-connected transition metal based SBB were successfully targeted and synthesized. These two synthetic platforms will be presented and used as examples of how these design methods have been (and can be further) utilized to modify existing materials or develop new materials for gas storage and

  9. Liquid-Phase Synthesis of 2'-Methyl-RNA on a Homostar Support through Organic-Solvent Nanofiltration.

    Science.gov (United States)

    Gaffney, Piers R J; Kim, Jeong F; Valtcheva, Irina B; Williams, Glynn D; Anson, Mike S; Buswell, Andrew M; Livingston, Andrew G

    2015-06-22

    Due to the discovery of RNAi, oligonucleotides (oligos) have re-emerged as a major pharmaceutical target that may soon be required in ton quantities. However, it is questionable whether solid-phase oligo synthesis (SPOS) methods can provide a scalable synthesis. Liquid-phase oligo synthesis (LPOS) is intrinsically scalable and amenable to standard industrial batch synthesis techniques. However, most reported LPOS strategies rely upon at least one precipitation per chain extension cycle to separate the growing oligonucleotide from reaction debris. Precipitation can be difficult to develop and control on an industrial scale and, because many precipitations would be required to prepare a therapeutic oligonucleotide, we contend that this approach is not viable for large-scale industrial preparation. We are developing an LPOS synthetic strategy for 2'-methyl RNA phosphorothioate that is more amenable to standard batch production techniques, using organic solvent nanofiltration (OSN) as the critical scalable separation technology. We report the first LPOS-OSN preparation of a 2'-Me RNA phosphorothioate 9-mer, using commercial phosphoramidite monomers, and monitoring all reactions by HPLC, (31)P NMR spectroscopy and MS.

  10. High Throughput and High Speed Organic Synthesis in Drug Discovery:An Integration of Chemistry and Technology

    Institute of Scientific and Technical Information of China (English)

    Li Chen

    2004-01-01

    Drug discovery is a complicated process that involves multiple synthetic chemistry tasks.Among them, lead generation and optimization is the core business in the discovery research.During the stage of lead generation, a large library of many thousands individual compounds will be screened against a biological target to identify a set of hits that showed desirable activity. Once a hit has been identified, analog synthesis and development of SAR around this hit and establishment of relationship between targeted protein and its cellular function become the key activity in the drug discovery project. During this process, focused libraries of a few hundred compounds (X00) will be synthesized and tested. For synthetic chemistry tasks, the efficiency can be enhanced through "parallel processing or high throughput chemisay" using automation technology with which a large number of compounds can be synthesized, purified and plated at same time for biological and pharmaceutical screenings. To accelerate the lead optimization high speed synthesis is conducted when necessary and to improve "single process" efficiency using automation technology, when the rate limiting step become developing synthetic method to produce large amount of compounds (in gram quantity) that can be used in vivo pharmacology study. With these in mind, we designed integrated HTC technology platform which supports the key chemical synthesis activities in discovery research. In this presentation, several examples will be presented to illustrate the applications of high throughput and high speed organic synthesis in drug discovery.

  11. How does the general public view posthumous organ donation? A meta-synthesis of the qualitative literature

    Directory of Open Access Journals (Sweden)

    Newton Joshua D

    2011-10-01

    Full Text Available Abstract Background Many individuals are unwilling to become posthumous organ donors, resulting in a disparity between the supply and demand for organ transplants. A meta-synthesis of the qualitative literature was therefore conducted to determine how the general public views posthumous organ donation. Methods Three online databases (PubMed, PsycINFO, Scopus were searched for articles published between January 1990 and May 2008 using the following search terms: organ donation, qualitative, interview. Eligibility criteria were: examination of beliefs about posthumous organ donation; utilization of a qualitative research design; and publication in an English peer-reviewed journal. Exclusion criteria were examining how health professionals or family members of organ donors viewed posthumous organ donation. Grounded theory was used to identify the beliefs emerging from this literature. Thematically-related beliefs were then grouped to form themes. Results 27 articles from 24 studies met the inclusion criteria and were reviewed. The major themes identified were: religion, death, altruism, personal relevance, the body, the family, medical professionals, and transplant recipients. An altruistic motivation to help others emerged as the most commonly identified motivator for becoming an organ donor, although feeling a sense of solidarity with the broader community and believing that donated organs are put to good use may be important preconditions for the emergence of this motivation. The two most commonly identified barriers were the need to maintain bodily integrity to safeguard progression into the afterlife and the unethical recovery of organs by medical professionals. The influence of stakeholder groups on willingness to become an organ donor was also found to vary by the level of control that each stakeholder group exerted over the donation recovery process and their perceived conflict of interest in wanting organ donation to proceed. Conclusions

  12. Post-Synthesis Functionalization of Porous Organic Polymers for CO2 Capture

    KAUST Repository

    Al Otaibi, Mona S.

    2014-07-01

    Solid porous materials are network materials that contain space void. Porous Organic Polymers (POPs) are porous materials, which are constructed from organic building blocks and exhibit large surface area with low densities. Due to these characteristics, POPs have attracted attentions because of their potential use in application such as gas storage and chemical separation. This thesis presents a study of the synthesis of novel POP being a network based on 2,5- dibromobenzaldehyde and 1,3,5-triethynylbenzene linked together via Sonogashira- Hagihara (SH) coupling. This network showed a relatively good surface area of 770 m2/g and total pore volume of 0.59 cc/g. In addition, it proved to be chemically and thermally stable, maintaining the thermal stability up to 350oC. In addition to synthesize novel aldehyde-POP network, it was also possible to post synthetically modify a network via one-step post synthetic functionalization by amine. Ethelynediamine (EDA), Diethylenetriamine (DETA), and Tris(2-aminoethyl)amine (Tris-amine) are three different amines used for aldehyde-POP functionalization. The produced networks were aminated via different amine species substitution the aldehyde group present within the network. Modification to these networks resulted in a decrease in surface area from 770 m2.g-1 to 333 m2.g-1, 162 m2.g-1, and 211 m2.g-1 in respective to EDA, DETA, and Tris-amine. Although the surface areas were decreased, the CO2 adsorption was enhanced as evidenced by the increase of Qst (i.e., from 25 to 45 kJ.mol-1 for DETA at low coverage). Our findings are expected to strengthen existing research areas of the influence of different type of amines (e.g aromatic amine) on CO2 adsorption. Although amine grafting has been studied in other systems (e.g., PAFs and MOFs), we are the first to reported amine functionalized POPs using a novel one-step amine grafting PSM procedure. Future research might extend to study the interaction between CO2 and amine species under

  13. Molecular characterization of BZR transcription factor family and abiotic stress induced expression profiling in Brassica rapa.

    Science.gov (United States)

    Saha, Gopal; Park, Jong-In; Jung, Hee-Jeong; Ahmed, Nasar Uddin; Kayum, Md Abdul; Kang, Jong-Goo; Nou, Ill-Sup

    2015-07-01

    BRASSINAZOLE-RESISTANT (BZR) transcription factors (TFs) are primarily well known as positive regulators of Brassinosteroid (BR) signal transduction in different plants. BR is a plant specific steroid hormone, which has multiple stress resistance functions besides various growth regulatory roles. Being an important regulator of the BR synthesis, BZR TFs might have stress resistance related activities. However, no stress resistance related functional study of BZR TFs has been reported in any crop plants so far. Therefore, this study identified 15 BZR TFs of Brassica rapa (BrBZR) from a genome-wide survey and characterized them through sequence analysis and expression profiling against several abiotic stresses. Various systematic in silico analysis of these TFs validated the fundamental properties of BZRs, where a high degree of similarity also observed with recognized BZRs of other plant species from the comparison studies. In the organ specific expression analyses, 6 BrBZR TFs constitutively expressed in flower developmental stages indicating their flower specific functions. Subsequently, from the stress resistance related expression profiles differential transcript abundance levels were observed by 6 and 11 BrBZRs against salt and drought stresses, respectively. All BrBZRs showed several folds up-regulation against exogenous ABA treatment. All BrBZRs also showed differential expression against low temperature stress treatments and these TFs were proposed as transcriptional activators of CBF cold response pathway of B. rapa. Notably, three BrBZRs gave co-responsive expression against all the stresses tested here, suggesting their multiple stress resistance related functions. Thus, the findings would be helpful in resolving the complex regulatory mechanism of BZRs in stress resistance and further functional genomics study of these potential TFs in different Brassica crops. PMID:25931321

  14. Organic synthesis in the Smith Group: a personal selection of a dozen lessons learned at the University of Pennsylvania.

    Science.gov (United States)

    Minbiole, Kevin P C

    2016-04-01

    The passionate study of the complex and ever-evolving discipline of organic synthesis over more than a four-decade span is certain to elucidate meaningful and significant lessons. Over this period, Amos B. Smith III, the Rhodes-Thompson Professor of Chemistry and Member of the Monell Chemical Senses Center at the University of Pennsylvania, has mentored well over 100 doctoral and masters students, more than 200 postdoctoral associates and numerous undergraduates, in addition to collaborating with a wide spectrum of internationally recognized scholars. His research interests, broadly stated, comprise complex molecule synthesis, the development of new, versatile and highly effective synthetic methods, bioorganic and medicinal chemistry, peptide mimicry chemistry and material science. Each area demands a high level of synthetic design and execution. United by a passion to unlock the secrets of organic synthesis, and perhaps of Nature itself, innumerable lessons have been, and continue to be, learned by the members of the Smith Group. This lead article in a Special Issue of the Journal of Antibiotics affords an opportunity to share some of those lessons learned, albeit a small selection of personal favorites.

  15. Evaluation of Abiotic Resource LCIA Methods

    Directory of Open Access Journals (Sweden)

    Rodrigo A. F. Alvarenga

    2016-02-01

    Full Text Available In a life cycle assessment (LCA, the impacts on resources are evaluated at the area of protection (AoP with the same name, through life cycle impact assessment (LCIA methods. There are different LCIA methods available in literature that assesses abiotic resources, and the goal of this study was to propose recommendations for that impact category. We evaluated 19 different LCIA methods, through two criteria (scientific robustness and scope, divided into three assessment levels, i.e., resource accounting methods (RAM, midpoint, and endpoint. In order to support the assessment, we applied some LCIA methods to a case study of ethylene production. For RAM, the most suitable LCIA method was CEENE (Cumulative Exergy Extraction from the Natural Environment (but SED (Solar Energy Demand and ICEC (Industrial Cumulative Exergy Consumption/ECEC (Ecological Cumulative Exergy Consumption may also be recommended, while the midpoint level was ADP (Abiotic Depletion Potential, and the endpoint level was both the Recipe Endpoint and EPS2000 (Environmental Priority Strategies. We could notice that the assessment for the AoP Resources is not yet well established in the LCA community, since new LCIA methods (with different approaches and assessment frameworks are showing up, and this trend may continue in the future.

  16. SYNTHESIS OF ORGANIC EPOXIDES USING A SPINNING TUBE-IN-TUBE REACTOR

    Science.gov (United States)

    The U.S. Environmental Protectiion Agency (USEPA) and Kreido Laboratories have established a Cooperative Research and Development Agreement (CRADA) collaboration, to develop and commercialize green and sustainable chemistries in the area of industrial chemcial synthesis. The STT...

  17. Synthesis of Meso-Octamethylporphyrinogen: An Undergraduate Laboratory Mini-Scale Experiment in Organic Heterocyclic Chemistry

    Science.gov (United States)

    Sobral, Abilio J. F. N.

    2005-01-01

    The synthesis of meso-octamethylporphyrinogen that involves a mini-scale preparation and uses acetone as reactant and also as solvent is presented. It results in a product of almost analytical grade directly from the reaction medium.

  18. Synthesis of many different types of organic small molecules using one automated process.

    Science.gov (United States)

    Li, Junqi; Ballmer, Steven G; Gillis, Eric P; Fujii, Seiko; Schmidt, Michael J; Palazzolo, Andrea M E; Lehmann, Jonathan W; Morehouse, Greg F; Burke, Martin D

    2015-03-13

    Small-molecule synthesis usually relies on procedures that are highly customized for each target. A broadly applicable automated process could greatly increase the accessibility of this class of compounds to enable investigations of their practical potential. Here we report the synthesis of 14 distinct classes of small molecules using the same fully automated process. This was achieved by strategically expanding the scope of a building block-based synthesis platform to include even C(sp3)-rich polycyclic natural product frameworks and discovering a catch-and-release chromatographic purification protocol applicable to all of the corresponding intermediates. With thousands of compatible building blocks already commercially available, many small molecules are now accessible with this platform. More broadly, these findings illuminate an actionable roadmap to a more general and automated approach for small-molecule synthesis.

  19. Layer-by-Layer Method for the Synthesis and Growth of Surface Mounted Metal-Organic Frameworks (SURMOFs

    Directory of Open Access Journals (Sweden)

    Osama Shekhah

    2010-02-01

    Full Text Available A layer-by-layer method has been developed for the synthesis of metal-organic frameworks (MOFs and their deposition on functionalized organic surfaces. The approach is based on the sequential immersion of functionalized organic surfaces into solutions of the building blocks of the MOF, i.e., the organic ligand and the inorganic unit. The synthesis and growth of different types of MOFs on substrates with different functionalization, like COOH, OH and pyridine terminated surfaces, were studied and characterized with different surface characterization techniques. A controlled and highly oriented growth of very homogenous films was obtained using this method. The layer-by-layer method offered also the possibility to study the kinetics of film formation in more detail using surface plasmon resonance and quartz crystal microbalance. In addition, this method demonstrates the potential to synthesize new classes of MOFs not accessible by conventional methods. Finally, the controlled growth of MOF thin films is important for many applications like chemical sensors, membranes and related electrodes.

  20. Synthesis and Characterization of Organic Impurities in Bortezomib Anhydride Produced by a Convergent Technology

    Science.gov (United States)

    Ivanov, Andrey S.; Shishkov, Sergey V.; Zhalnina, Anna A.

    2012-01-01

    A profile of impurities in bortezomib anhydride, produced by a recently developed convergent technology, has been characterized. HPLC-MS analysis of the drug essence revealed three impurities: an epimer of bortezomib, resulting from partial racemization of l-phenylalanine’s stereogenic center during the chemical synthesis, and two epimeric products of oxidative degradation of bortezomib, in which boron is replaced by the OH group. The impurities were obtained by chemical synthesis and characterized by physical methods. PMID:22396904

  1. Sonication-induced pathways in the synthesis of light-active catalysts for photocatalytic oxidation of organic contaminants.

    Science.gov (United States)

    Colmenares, Juan Carlos

    2014-06-01

    Heterogeneous photocatalysis is becoming increasingly important due to the variety of its applications and multidisciplinary aspects. Applications such as water/air detoxification-disinfection, solar-energy storage, high-value-chemical production, optoelectronics, and sensors are some of the most promising. In recent years, the development of environmentally-friendly and cost-efficient procedures for material synthesis that could substitute the old ones has been on demand. Unconventional and soft techniques, such as sonication, offer enormous possibilities for the synthesis of a broad spectrum of nanostructured materials, among them photocatalysts. This Review will focus the readers' attention on ultrasound-induced methodologies used for the preparation of nanostructured photocatalysts (e.g., supported nanoparticles, semiconductors) and their application in the photocatalytic oxidation of organic contaminants.

  2. Synthesis of a Sulfonated Two-Dimensional Covalent Organic Framework as an Efficient Solid Acid Catalyst for Biobased Chemical Conversion.

    Science.gov (United States)

    Peng, Yongwu; Hu, Zhigang; Gao, Yongjun; Yuan, Daqiang; Kang, Zixi; Qian, Yuhong; Yan, Ning; Zhao, Dan

    2015-10-12

    Because of limited framework stability tolerance, de novo synthesis of sulfonated covalent organic frameworks (COFs) remains challenging and unexplored. Herein, a sulfonated two-dimensional crystalline COF, termed TFP-DABA, was synthesized directly from 1,3,5-triformylphloroglucinol and 2,5-diaminobenzenesulfonic acid through a previously reported Schiff base condensation reaction, followed by irreversible enol-to-keto tautomerization, which strengthened its structural stability. TFP-DABA is a highly efficient solid acid catalyst for fructose conversion with remarkable yields (97 % for 5-hydroxymethylfurfural and 65 % for 2,5-diformylfuran), good chemoselectivity, and good recyclability. The present study sheds light on the de novo synthesis of sulfonated COFs as novel solid acid catalysts for biobased chemical conversion.

  3. Bringing the science of proteins into the realm of organic chemistry: total chemical synthesis of SEP (synthetic erythropoiesis protein).

    Science.gov (United States)

    Kent, Stephen B H

    2013-11-11

    Erythropoietin, commonly known as EPO, is a glycoprotein hormone that stimulates the production of red blood cells. Recombinant EPO has been described as "arguably the most successful drug spawned by the revolution in recombinant DNA technology". Recently, the EPO glycoprotein molecule has re-emerged as a major target of synthetic organic chemistry. In this article I will give an account of an important body of earlier work on the chemical synthesis of a designed EPO analogue that had full biological activity and improved pharmacokinetic properties. The design and synthesis of this "synthetic erythropoiesis protein" was ahead of its time, but has gained new relevance in recent months. Here I will document the story of one of the major accomplishments of synthetic chemistry in a more complete way than is possible in the primary literature, and put the work in its contemporaneous context.

  4. Synthesis of a Sulfonated Two-Dimensional Covalent Organic Framework as an Efficient Solid Acid Catalyst for Biobased Chemical Conversion.

    Science.gov (United States)

    Peng, Yongwu; Hu, Zhigang; Gao, Yongjun; Yuan, Daqiang; Kang, Zixi; Qian, Yuhong; Yan, Ning; Zhao, Dan

    2015-10-12

    Because of limited framework stability tolerance, de novo synthesis of sulfonated covalent organic frameworks (COFs) remains challenging and unexplored. Herein, a sulfonated two-dimensional crystalline COF, termed TFP-DABA, was synthesized directly from 1,3,5-triformylphloroglucinol and 2,5-diaminobenzenesulfonic acid through a previously reported Schiff base condensation reaction, followed by irreversible enol-to-keto tautomerization, which strengthened its structural stability. TFP-DABA is a highly efficient solid acid catalyst for fructose conversion with remarkable yields (97 % for 5-hydroxymethylfurfural and 65 % for 2,5-diformylfuran), good chemoselectivity, and good recyclability. The present study sheds light on the de novo synthesis of sulfonated COFs as novel solid acid catalysts for biobased chemical conversion. PMID:26448524

  5. Mesoporous Silica Based Gold Catalysts: Novel Synthesis and Application in Catalytic Oxidation of CO and Volatile Organic Compounds (VOCs

    Directory of Open Access Journals (Sweden)

    Leonarda F. Liotta

    2013-10-01

    Full Text Available Gold nanoparticles, particularly with the particle size of 2–5 nm, have attracted increasing research attention during the past decades due to their surprisingly high activity in CO and volatile organic compounds (VOCs oxidation at low temperatures. In particular, CO oxidation below room temperature has been extensively studied on gold nanoparticles supported on several oxides (TiO2, Fe2O3, CeO2, etc.. Recently, mesoporous silica materials (such as SBA-15, MCM-41, MCM-48 and HMS possessing ordered channel structures and suitable pore diameters, large internal surface areas, thermal stabilities and excellent mechanical properties, have been investigated as suitable hosts for gold nanoparticles. In this review we highlight the development of novel mesoporous silica based gold catalysts based on examples, mostly from recently reported results. Several synthesis methods are described herein. In detail we report: the modification of silica with organic functional groups; the one-pot synthesis with the incorporation of both gold and coupling agent containing functionality for the synthesis of mesoporous silica; the use of cationic gold complexes; the synthesis of silica in the presence of gold colloids or the dispersion of gold colloids protected by ligands or polymers onto silica; the modification of silica by other metal oxides; other conventional preparation methods to form mesoporous silica based gold catalysts. The gold based catalysts prepared as such demonstrate good potential for use in oxidation of CO and VOCs at low temperatures. From the wide family of VOCs, the oxidation of methanol and dimethyldisulfide has been addressed in the present review.

  6. The abiotic litter decomposition in the drylands

    Science.gov (United States)

    Lee, H.; Throop, H.; Rahn, T. A.

    2009-12-01

    The decomposition of litter is an important ecosystem function that controls carbon and nutrient cycling, which is well understood from the relationship between temperature and moisture. However, the decomposition in the arid and semiarid environments (hereafter drylands) is relatively poorly predicted due to several abiotic factors such as the effect of ultraviolet radiation and physical mixing of fallen litter with soil. The relative magnitude of these abiotic factors to ecosystem scale litter decomposition is still in debate. Here, we examine the effect of two major abiotic factors in the drylands litter decomposition by conducting a controlled laboratory study using plant litter and soil collected from Sonoran and Chihuahuan desert areas. The first part of the experiment focused on the effect of soil-litter mixing. We established a complete block design of three levels of soil and litter mixing (no mixing, light soil-litter mixing, and complete soil-litter mixing) in combination with three levels of soil moisture (1%, 2%, and 6% volumetric water content) using 2g of two most dominant species litter, grass and mesquite, and 50g of air-dried soils in 500ml mason jar and incubated them under 25C. We measured CO2 fluxes from these soil-litter incubations and harvested the soil and litter at 0, 1, 2, 4, 8, and 16 weeks and analyzed them of carbon and nitrogen content as well as the actual mass loss in the litter. The second part of the experiment focused on the effect of ultraviolet radiation. We established short-term litter incubation on a quartz chamber and used different temperature, moisture, and minerals to find the mechanism of photodegradation of litter. We measured CO2 fluxes from the litter incubation under ultraviolet radiation and also measured 13CO2 from these emissions. We were able to detect changes in the rate of carbon mineralization as a result of our treatments in the first week of soil-litter mixing experiment. The carbon mineralization rate was

  7. Generation of RNA in abiotic conditions.

    Science.gov (United States)

    di Mauro, Ernesto

    Generation of RNA in abiotic conditions. Ernesto Di Mauro Dipartimento di Genetica Bi-ologia Molecolare, Universit` "Sapienza" Roma, Italy. a At least four conditions must be satisfied for the spontaneous generation of (pre)-genetic poly-mers: 1) availability of precursors that are activated enough to spontaneously polymerize. Preliminary studies showed that (a) nucleic bases and acyclonucleosides can be synthesized from formamide H2NCOH by simply heating with prebiotically available mineral catalysts [last reviewed in (1)], and that b) nucleic bases can be phosphorylated in every possible posi-tion [2'; 3'; 5'; cyclic 2',3'; cyclic 3',5' (2)]. The higher stability of the cyclic forms allows their accumulation. 2) A polymerization mechanism. A reaction showing the formation of RNA polymers starting from prebiotically plausible precursors (3',5' cyclic GMP and 3', 5'cyclic AMP) was recently reported (3). Polymerization in these conditions is thermodynamically up-hill and an equilibrium is attained that limits the maximum length of the polymer produced to about 40 nucleotides for polyG and 100 nucleotides for polyA. 3) Ligation of the synthesized oligomers. If this type of reaction could occur according to a terminal-joining mechanism and could generate canonical 3',5' phosphodiester bonds, exponential growth would be obtained of the generated oligomers. This type of reaction has been reported (4) , limited to homogeneous polyA sequences and leading to the production of polyA dimers and tetramers. What is still missing are: 4) mechanisms that provide the proof of principle for the generation of sequence complexity. We will show evidence for two mechanisms providing this proof of principle for simple complementary sequences. Namely: abiotic sequence complementary-driven terminal ligation and sequence-complementary terminal growth. In conclusion: all the steps leading to the generation of RNA in abiotic conditions are satisfied. (1) R Saladino, C Crestini, F

  8. Template Directed Synthesis and Characterization of Organic Mesoporous Polymers and their Adsorption Performance for Lysozyme

    Science.gov (United States)

    Sridhar, Manasa

    bimodal mesophases and the tertiary pore size resulting from the dissolution of silica pore walls. The organic, biocompatible MPFFs were employed as sorbents for Lysozyme immobilization at ambient temperature and under isoelectric condition. MPFFs exhibiting loading capacities of more than 230 mg/g serve to be highly encouraging in pursuing our interests further to achieve even higher uptake through post-synthesis functionalization.

  9. Multi-enzyme co-embedded organic-inorganic hybrid nanoflowers: synthesis and application as a colorimetric sensor.

    Science.gov (United States)

    Sun, Jiayu; Ge, Jiechao; Liu, Weimin; Lan, Minhua; Zhang, Hongyan; Wang, Pengfei; Wang, Yanming; Niu, Zhongwei

    2014-01-01

    This study reports a facile method for the synthesis of multi-enzyme co-embedded organic-inorganic hybrid nanoflowers, using glucose oxidase (GOx) and horseradish peroxidase (HRP) as the organic components, and Cu3(PO4)2 · 3H2O as the inorganic component. The synthesized nanoflowers enable the combination of a two-enzyme cascade reaction in one step, in which the GOx component of the nanoflowers oxidizes glucose to generate H2O2, which then reacts with the adjacent HRP component on the nanoflowers to oxidize the chromogenic substrates, resulting in an apparent color change. Given the close proximity of the two enzyme components in a single nanoflower, this novel sensor greatly reduces the diffusion and decomposition of H2O2, and greatly enhances the sensitivity of glucose detection. Thus, the obtained multi-enzyme co-embedded organic-inorganic hybrid nanoflowers can be unquestionably used as highly sensitive colorimetric sensors for the detection of glucose. Notably, this work presents a very facile route for the synthesis of multi-enzyme co-embedded nanomaterials for the simultaneous catalysis of multi-step cascade enzymatic reactions. Furthermore, it has great potential for application in biotechnology, and biomedical and environmental chemistry.

  10. Self-assembly versus stepwise synthesis: heterometal-organic frameworks based on metalloligands with tunable luminescence properties.

    Science.gov (United States)

    Zhang, Shu-Ran; Du, Dong-Ying; Tan, Ke; Qin, Jun-Sheng; Dong, Hui-Qing; Li, Shun-Li; He, Wen-Wen; Lan, Ya-Qian; Shen, Ping; Su, Zhong-Min

    2013-08-19

    A new family of heterometal-organic frameworks has been prepared by two synthesis strategies, in which IFMC-26 and IFMC-27 are constructed by self-assembly and IFMC-28 is obtained by stepwise synthesis based on the metalloligand (IFMC=Institute of Functional Material Chemistry). IFMC-26 is a (3,6)-connected net and IFMC-27 is a (4,8)-connected 3D framework. The metalloligands {Ni(H4 L)}(NO3 )2 are connected by binuclear lanthanide clusters giving rise to a 2D sheet structure in IFMC-28. Notably, IFMC-26-Eux Tby and IFMC-28-Eux Tby have been obtained by changing the molar ratios of raw materials. Owing to the porosity of IFMC-26, Tb(3+) @IFMC-26-Eu and Eu(3+) @IFMC-26-Tb are obtained by postencapsulating Tb(III) and Eu(III) ions into the pores, respectively. Tunable luminescence in metal-organic frameworks is achieved by the two kinds of doping methods. In particular, the quantum yields of heterometal-organic frameworks are apparently enhanced by postencapsulation of Ln(III) ions.

  11. A significant abiotic pathway for the formation of unknown nitrogen in nature

    Science.gov (United States)

    Jokic, A.; Schulten, H.-R.; Cutler, J. N.; Schnitzer, M.; Huang, P. M.

    2004-03-01

    The global nitrogen cycle is of prime importance in natural ecosystems. However, the origin and nature of up to one-half of total soil N remains obscure despite all attempts at elucidation. Our data provide, for the first time, unequivocal evidence that the promoting action of Mn (IV) oxide on the Maillard reaction (sugar-amino acid condensation) under ambient conditions results in the abiotic formation of heterocyclic N compounds, which are often referred to as unknown nitrogen, and of amides which are apparently the dominant N moieties in nature. The information presented is of fundamental significance in understanding the role of mineral colloids in abiotic transformations of organic N moieties, the incorporation of N in the organic matrix of fossil fuels, and the global N cycle.

  12. Synthesis and Characterization of Metal-Organic Frameworks (MOFs) for Photon Collection and Energy Transfer

    Science.gov (United States)

    So, Monica C.

    Projected global energy demand is widely believed to reach 30 TW by 2050. Currently, fossil fuels collectively represent over 80% of our total energy supply, while only 10% come from renewable sources. To meet future demands, however, we must maximize our use of renewable resources while minimizing our dependence on fossil fuels. While there are many sources of renewable energy, solar energy is one of the most abundant; in fact, the sun delivers up to 67 TW of power annually, which exceeds the projected energy demand in 2050. While there are multiple ways to convert sunlight to electricity, organic photovoltaics (OPVs) has the shortest energy payback time; this is the time required for the PV module to generate the equivalent amount of energy that originally was used to manufacture the PV module. OPVs show promise for light-to-electrical energy conversion with the best performing cells having power conversion efficiencies of 8%, but the theoretical maximum is at 32%. If efficiencies can be increased to even a fraction of the way to ˜16%, OPVs would be more cost-competitive with their inorganic counterparts. However, there are four major challenges in improving OPV performance. These include (a) poor light harvesting, due to a limited range of absorbance of visible light, (b) inefficient exciton splitting into holes and electrons, due to the limited diffusion length of excitons (typically ca. 10 nm), (c) increased recombination of separated charges at the donor/acceptor interface, and (d) inefficient collection of charges at the active layer/electrode interface (i.e. partial electrical shorting). OPVs constructed from conventional materials and architectures involve conflicting design requirements; this makes it impossible to address all four problems simultaneously. The projects described in this dissertation involve the design, synthesis, and characterization of a new class of OPV materials that have the potential to overcome the problems with conventional cells

  13. Synthesis of a Partially Protected Azidodeoxy Sugar. A Project Suitable for the Advanced Undergraduate Organic Chemistry Laboratory

    Science.gov (United States)

    Norris, Peter; Freeze, Scott; Gabriel, Christopher J.

    2001-01-01

    The synthetic chemistry of carbohydrates provides a wealth of possible experiments for the undergraduate organic chemistry laboratory. However, few appropriate examples have been developed to date. With this simple two-step synthesis of a partially protected azidodeoxy sugar, we demonstrate several important concepts introduced in undergraduate chemistry (alcohol activation, steric hindrance, nucleophilic substitution) while offering products that are readily amenable to analysis by high field NMR. Students are exposed to techniques such as monitoring reactions by TLC, workup of reaction mixtures, and isolation by flash chromatography. Suitable methods for analysis of products include NMR, IR, MS, and polarimetry.

  14. N-Heterocyclic carbene/Brønsted acid cooperative catalysis as a powerful tool in organic synthesis

    Directory of Open Access Journals (Sweden)

    Rob De Vreese

    2012-03-01

    Full Text Available The interplay between metals and N-heterocyclic carbenes (NHCs has provided a window of opportunities for the development of novel catalytic strategies within the past few years. The recent successful combination of Brønsted acids with NHCs has added a new dimension to the field of cooperative catalysis, enabling the stereoselective synthesis of functionalized pyrrolidin-2-ones as valuable scaffolds in heterocyclic chemistry. This Commentary will briefly highlight the concept of N-heterocyclic carbene/Brønsted acid cooperative catalysis as a new and powerful methodology in organic chemistry.

  15. N-Heterocyclic carbene/Brønsted acid cooperative catalysis as a powerful tool in organic synthesis

    Science.gov (United States)

    De Vreese, Rob

    2012-01-01

    Summary The interplay between metals and N-heterocyclic carbenes (NHCs) has provided a window of opportunities for the development of novel catalytic strategies within the past few years. The recent successful combination of Brønsted acids with NHCs has added a new dimension to the field of cooperative catalysis, enabling the stereoselective synthesis of functionalized pyrrolidin-2-ones as valuable scaffolds in heterocyclic chemistry. This Commentary will briefly highlight the concept of N-heterocyclic carbene/Brønsted acid cooperative catalysis as a new and powerful methodology in organic chemistry. PMID:22509208

  16. Novel Easy Preparations of Some Aromatic Iodine(I, III, and V Reagents, Widely Applied in Modern Organic Synthesis

    Directory of Open Access Journals (Sweden)

    Lech Skulski

    2003-01-01

    Full Text Available We report our novel (or considerably improved methods for the synthesis of aromatic iodides, (dichloroiodoarenes, (diacetoxyiodoarenes, [bis(trifluoroacetoxy-iodo]arenes, iodylarenes and diaryliodonium salts, as well as some facile, oxidative anion metatheses in crude diaryliodonium or tetraalkylammonium halides and, for comparison, potassium halides. All our formerly published papers were discussed and explained in our review “Organic Iodine(I, III, and V Chemistry: 10 Years of Development at the Medical University of Warsaw, Poland” (1990-2000 [1]. Our newest results are discussed below.

  17. Transforming growth factor-beta 1 stimulates synthesis of proteoglycan aggregates in calf articular cartilage organ cultures

    Energy Technology Data Exchange (ETDEWEB)

    Morales, T.I. (Bone Research Branch, National Institute of Dental Research, National Institutes of Health, Bethesda, MD (United States))

    1991-04-01

    Previous work showed that transforming growth factor-beta 1 (TGF-beta 1), added alone to bovine cartilage organ cultures, stimulated (35S)sulfate incorporation into macromolecular material but did not investigate the fidelity of the stimulated system to maintain synthesis of cartilage-type proteoglycans. This paper provides evidence that chondrocytes synthesize the appropriate proteoglycan matrix under TGF-beta 1 stimulation: (1) there is a coordinated increase in hyaluronic acid and proteoglycan monomer synthesis, (2) link-stable proteoglycan aggregates are assembled, (3) the hybrid chondroitin sulfate/keratan sulfate monomeric species is synthesized, and (4) there is an increase in protein core synthesis. Some variation in glycosylation patterns was observed when proteoglycans synthesized under TGF-beta 1 stimulation were compared to those synthesized under basal conditions. Thus comparing TGF-beta 1 to basal samples respectively, the monomers were larger (Kav on Sepharose CL-2B = 0.29 vs 0.41), the chondroitin sulfate chains were longer by approximately 3.5 kDa, the percentage of total glycosaminoglycan in keratan sulfate increased slightly from approximately 4% (basal) to approximately 6%, and the unsulfated disaccharide decreased from 28% (basal) to 12%. All of these variations are in the direction of a more anionic proteoglycan. Since the ability of proteoglycans to confer resiliency to the cartilage matrix is directly related to their anionic nature, these changes would presumably have a beneficial effect on tissue function.

  18. Soft templating strategies for the synthesis of mesoporous materials: inorganic, organic-inorganic hybrid and purely organic solids.

    Science.gov (United States)

    Pal, Nabanita; Bhaumik, Asim

    2013-03-01

    With the discovery of MCM-41 by Mobil researchers in 1992 the journey of the research on mesoporous materials started and in the 21st century this area of scientific investigation have extended into numerous branches, many of which contribute significantly in emerging areas like catalysis, energy, environment and biomedical research. As a consequence thousands of publications came out in large varieties of national and international journals. In this review, we have tried to summarize the published works on various synthetic pathways and formation mechanisms of different mesoporous materials viz. inorganic, organic-inorganic hybrid and purely organic solids via soft templating pathways. Generation of nanoscale porosity in a solid material usually requires participation of organic template (more specifically surfactants and their supramolecular assemblies) called structure-directing agent (SDA) in the bottom-up chemical reaction process. Different techniques employed for the syntheses of inorganic mesoporous solids, like silicas, metal doped silicas, transition and non-transition metal oxides, mixed oxides, metallophosphates, organic-inorganic hybrids as well as purely organic mesoporous materials like carbons, polymers etc. using surfactants are depicted schematically and elaborately in this paper. Moreover, some of the frontline applications of these mesoporous solids, which are directly related to their functionality, composition and surface properties are discussed at the appropriate places.

  19. Process design for enzymatic peptide synthesis in near-anhydrous organic media

    NARCIS (Netherlands)

    Vossenberg, P.; Beeftink, H.H.; Stuart, M.A.C.; Tramper, J.

    2013-01-01

    This work is a case study on a process design for enzymatic peptide synthesis, which is based on and inspired by previously established data about the Alcalase-catalyzed coupling of an amino acid amide and a chemically synthesized activated N-protected amino acid carbamoylmethyl ester in near-anhydr

  20. Total Synthesis and Structure-Activity Relationship of Glycoglycerolipids from Marine Organisms

    Directory of Open Access Journals (Sweden)

    Jun Zhang

    2014-06-01

    Full Text Available Glycoglycerolipids occur widely in natural products, especially in the marine species. Glycoglycerolipids have been shown to possess a variety of bioactivities. This paper will review the different methodologies and strategies for the synthesis of biological glycoglycerolipids and their analogs for bioactivity assay. In addition, the bioactivities and structure-activity relationship of the glycoglycerolipids are also briefly outlined.

  1. Enzymatic synthesis of polyol esters in aqueous-organic two-phase systems.

    NARCIS (Netherlands)

    Janssen, A.E.M.

    1993-01-01

    The last decade increasingly attention is paid to lipases as catalysts for synthesis of components, such as fatty acid-based surfactants, flavors, edible oil equivalents, monomers and polymers, and amides. In this thesis, the lipase-catalyzed esterification of polyols and fatty acids is described. T

  2. Performance of Alcalase formulations in near dry organic media: Effect of enzyme hydration on dipeptide synthesis

    NARCIS (Netherlands)

    Vossenberg, P.; Beeftink, H.H.; Nuijens, T.; Quaedflieg, P.J.L.M.; Cohen Stuart, M.A.; Tramper, J.

    2012-01-01

    The use of different Alcalase formulations for protease-catalyzed dipeptide synthesis was investigated by studying the coupling of the carbamoylmethyl ester of N-protected phenylalanine with phenylalanine amide in tetrahydrofuran in the presence of molecular sieves (i.e. under near dry conditions).

  3. Student-Fabricated Microfluidic Devices as Flow Reactors for Organic and Inorganic Synthesis

    Science.gov (United States)

    Feng, Z. Vivian; Edelman, Kate R.; Swanson, Benjamin P.

    2015-01-01

    Flow synthesis in microfluidic devices has been rapidly adapted in the pharmaceutical industry and in many research laboratories. Yet, the cost of commercial flow reactors is a major factor limiting the dissemination of this technology in the undergraduate curriculum. Here, we present a laboratory activity where students design and fabricate…

  4. A Multistep Synthesis Featuring Classic Carbonyl Chemistry for the Advanced Organic Chemistry Laboratory

    Science.gov (United States)

    Duff, David B.; Abbe, Tyler G.; Goess, Brian C.

    2012-01-01

    A multistep synthesis of 5-isopropyl-1,3-cyclohexanedione is carried out from three commodity chemicals. The sequence involves an aldol condensation, Dieckmann-type annulation, ester hydrolysis, and decarboxylation. No purification is required until after the final step, at which point gravity column chromatography provides the desired product in…

  5. Thiophene 1,1-dioxides as unique building blocks in modern organic synthesis and materials chemistry

    Energy Technology Data Exchange (ETDEWEB)

    Moiseev, Andrew M; Balenkova, Elizabeth S; Nenajdenko, Valentine G [Department of Chemistry, M.V. Lomonosov Moscow State University, Moscow (Russian Federation)

    2006-12-31

    Data on the synthesis, reactivity features and the key chemical transformations of thiophene 1,1-dioxides are summarised and described systematically. The attention is focused on recent achievements in the chemistry of thiophene dioxides concerning both their practical use and theoretical studies.

  6. The Synthesis of Third-order Optical Nonlinear Organic Polyheterocyclic Materials

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    Synthesis of the third-order nonlinear materials: bis (l,4-dihydroxynaphthalene)tetrathiafulvalene and bis (1,4-dialkoxylnaphthalene) tetrathiafulvalene has been achieved in four steps, starting from 2,3-dichloro-l,4-naphthaquinone. The matcrials exhibit larger third-order nonlinear optical susceptibilities X(3).

  7. APPLICATION OF THE SULFONATE ESTER GROUP AS A LINKER FOR SOLID PHASE ORGANIC SYNTHESIS

    Institute of Scientific and Technical Information of China (English)

    SUN Weimin; LUO Juntao; HUANG Wenqiang; ZHU Xiaoxia

    2001-01-01

    A use of Sulfonate ester as a linker in synthesis of ω-aminoalkanols was reported. Diols were tethered onto polystyryl sulfonyl chloride resin, yielding sulfonate resins (2). After cleaved by diethyl amine, diisopropylamine and propylamine respectively, three ω-aminoalkanols were obtained.

  8. The Synthesis of Third—order Optical Nonlinear Organic Polyheterocyclic Materials

    Institute of Scientific and Technical Information of China (English)

    JianRongGAO; LuBaiCHENG; 等

    2002-01-01

    Synthesis of the third-order nonlinear materials:bis (1,4-dihydroxynaphthalene) tetrathiafulvalene and bis (1,4-dialkoxylnaphthalene) tetrathiafulvalene has been achieved in four steps, starting from 2,3-dichloro-1,4-naphthaquinone. The materials exhibit larger third-order nonlinear optical susceptibilities χ.

  9. APPLICATION OF THE SULFONATE ESTER GROUP AS A LINKER FOR SOLID PHASE ORGANIC SYNTHESIS

    Institute of Scientific and Technical Information of China (English)

    SUNWeimin; ZHUXiaoxia; 等

    2001-01-01

    A use of sulfonate ester as a linker in synthesis of w-aminoalkanols was reporte.Diols were tethered onto polystyryl sulfonyl chloride resin,yielding sulfonate resins(2).After cleaved by diethyl amine,diisopropylamine and propylamine respectively,three w-aminoalkanlos were obtained.

  10. BASIC SYNTHESIS AND BIOLOGICAL ACTIVITY OF SOME PHOSPHORCONTATNING ORGANIC COMPOUNDS CONTAINING FRAGMENTS OF UREA AND TRYHLORETILAMID

    Directory of Open Access Journals (Sweden)

    Gushylyk B.

    2013-10-01

    Full Text Available Data about directions of synthesis and use of the phosphororganic compounds in technics, biology and medicine is presented in the paper. Antimicrobial activity of 51 phosphororganic salts and ilides containing urine and threechlor ethylenamide has been studied. Perspective of the development of effective antimicrobial substances has been determined

  11. Aplicação de α-oxoceteno ditiocetais em síntese orgânica Reactivity of α-oxoketene dithiocetals in organic synthesis

    Directory of Open Access Journals (Sweden)

    Geonir M. Siqueira

    2010-01-01

    Full Text Available The synthesis and reactivity of α-oxoketenes dithioacetals (S,S-acetals, general structure [(R¹C=OC(R²=C(SR³(SR4], are reported. We also showed the application of S,S acetals as synthons for efficient synthesis of isoxazoles, pyrazoles, indazoles, thiophenes, dithiol thiones, pyridines, pyrimidines and other heterocycles. This work aims to review the importance of α-oxoketenes dithioacetals in organic chemistry during the past few years.

  12. One-Step Synthesis and Characterization of N-Doped Carbon Nanodots for Sensing in Organic Media.

    Science.gov (United States)

    Cayuela, Angelina; Carrillo-Carrión, Carolina; Soriano, M Laura; Parak, Wolfgang J; Valcárcel, Miguel

    2016-03-15

    Photoluminescent nitrogen-doped carbon nanodots (N-doped CNDs) soluble in organic media are synthesized in a one-step synthesis from a single-source precursor (an amphiphilic polymer), which exhibits a very high quantum yield (QY = 78%), excitation wavelength-dependent emission, and upconversion emission properties. The evolution of N-doped CND formation is studied via ultraviolet-visible and photoluminescence spectroscopy. Their analytical application as an effective sensor for the direct determination of nitroaromatic explosives and byproducts is shown based on their selective response via a fluorescence quenching mechanism. The proposed method is validated in soil samples by directly using the sensor in organic media without any further treatment or additional functionalization, which is an interesting aspect for practical applications. PMID:26870878

  13. Atmospheric Prebiotic Chemistry and Organic Hazes

    Science.gov (United States)

    Trainer, Melissa G.

    2012-01-01

    Earth's atmospheric composition at the time of the origin of life is not known, but it has often been suggested that chemical transformation of reactive species in the atmosphere was a significant source of pre biotic organic molecules. Experimental and theoretical studies over the past half century have shown that atmospheric synthesis can yield molecules such as amino acids and nucleobases, but these processes are very sensitive to gas composition and energy source. Abiotic synthesis of organic molecules is more productive in reduced atmospheres, yet the primitive Earth may not have been as reducing as earlier workers assumed, and recent research has reflected this shift in thinking. This work provides a survey of the range of chemical products that can be produced given a set of atmospheric conditions, with a particular focus on recent reports. Intertwined with the discussion of atmospheric synthesis is the consideration of an organic haze layer, which has been suggested as a possible ultraviolet shield on the anoxic early Earth. Since such a haze layer - if formed - would serve as a reservoir for organic molecules, the chemical composition of the aerosol should be closely examined. The results highlighted here show that a variety of products can be formed in mildly reducing or even neutral atmospheres, demonstrating that contributions of atmospheric synthesis to the organic inventory on early Earth should not be discounted. This review intends to bridge current knowledge of the range of possible atmospheric conditions in the prebiotic environment and pathways for synthesis under such conditions by examining the possible products of organic chemistry in the early atmosphere.

  14. The "Virtual ChemLab" Project: A Realistic and Sophisticated Simulation of Organic Synthesis and Organic Qualitative Analysis

    Science.gov (United States)

    Woodfield, Brian F.; Andrus, Merritt B.; Waddoups, Gregory L.; Moore, Melissa S.; Swan, Richard; Allen, Rob; Bodily, Greg; Andersen, Tricia; Miller, Jordan; Simmons, Bryon; Stanger, Richard

    2005-01-01

    A set of sophisticated and realistic laboratory simulations is created for use in freshman- and sophomore-level chemistry classes and laboratories called 'Virtual ChemLab'. A detailed assessment of student responses is provided and the simulation's pedagogical utility is described using the organic simulation.

  15. Effects of minerals on feed degradation and protein synthesis by rumen micro-organisms in a dual effluent fermenter.

    Science.gov (United States)

    Broudiscou, L P; Papon, Y; Broudiscou, A F

    1999-01-01

    In dual outflow continuous fermenters on a 75:25 hay/barley diet, feed degradation and protein synthesis by mixed rumen microbes were tested in relation to the concentrations of HPO4(2-), HCO3- and Cl- and Na+/K+ ratio in artificial saliva, by applying a 16-run Franquart design, and by fitting second-order polynomial models. The HPO4(2-), HCO3-, Cl- concentrations and Na+/K+ ratio ranged from 0.1 to 4 g.L-1, from 0.5 to 7 g.L-1, from 0.1 to 0.5 g.L-1 and from 0.5 to 15 g.g-1, respectively. Buffer salts, particularly HPO4(2-), were the major factors while Cl- concentration had negligible effects on microbial metabolism. Maximal neutral detergent fibre, acid detergent fibre and organic matter degradabilities occurred at intermediate values of HPO4(2-) and HCO3- concentrations. The outflow of microbial protein and the efficiency of microbial protein synthesis, which varied from 26.2 to 37.1 g.N.kg-1 of organic matter truly degraded, reached minima at the centre of the experimental domain. PMID:10327453

  16. On-surface synthesis of single-layered two-dimensional covalent organic frameworks via solid-vapor interface reactions.

    Science.gov (United States)

    Liu, Xuan-He; Guan, Cui-Zhong; Ding, San-Yuan; Wang, Wei; Yan, Hui-Juan; Wang, Dong; Wan, Li-Jun

    2013-07-17

    Surface covalent organic frameworks (SCOFs), featured by atomic thick sheet with covalently bonded organic building units, are promised to possess unique properties associated with reduced dimensionality, well-defined in-plane structure, and tunable functionality. Although a great deal of effort has been made to obtain SCOFs with different linkages and building blocks via both "top-down" exfoliation and "bottom-up" surface synthesis approaches, the obtained SCOFs generally suffer a low crystallinity, which impedes the understanding of intrinsic properties of the materials. Herein, we demonstrate a self-limiting solid-vapor interface reaction strategy to fabricate highly ordered SCOFs. The coupling reaction is tailored to take place at the solid-vapor interface by introducing one precursor via vaporization to the surface preloaded with the other precursor. Following this strategy, highly ordered honeycomb SCOFs with imine linkage are obtained. The controlled formation of SCOFs in our study shows the possibility of a rational design and synthesis of SCOFs with desired functionality.

  17. Controlled Synthesis of Organic/Inorganic van der Waals Solid for Tunable Light-Matter Interactions.

    Science.gov (United States)

    Niu, Lin; Liu, Xinfeng; Cong, Chunxiao; Wu, Chunyang; Wu, Di; Chang, Tay Rong; Wang, Hong; Zeng, Qingsheng; Zhou, Jiadong; Wang, Xingli; Fu, Wei; Yu, Peng; Fu, Qundong; Najmaei, Sina; Zhang, Zhuhua; Yakobson, Boris I; Tay, Beng Kang; Zhou, Wu; Jeng, Horng Tay; Lin, Hsin; Sum, Tze Chien; Jin, Chuanhong; He, Haiyong; Yu, Ting; Liu, Zheng

    2015-12-16

    High-quality organic and inorganic van der Waals (vdW) solids are realized using methylammonium lead halide (CH3 NH3 PbI3 ) as the organic part (organic perovskite) and 2D inorganic monolayers as counterparts. By stacking on various 2D monolayers, the vdW solids exhibit dramatically different light emissions. Futhermore, organic/h-BN vdW solid arrays are patterned for red-light emission.

  18. Biocatalytic organic synthesis of optically pure (S)-scoulerine and berbine and benzylisoquinoline alkaloids.

    Science.gov (United States)

    Schrittwieser, Joerg H; Resch, Verena; Wallner, Silvia; Lienhart, Wolf-Dieter; Sattler, Johann H; Resch, Jasmin; Macheroux, Peter; Kroutil, Wolfgang

    2011-08-19

    A chemoenzymatic approach for the asymmetric total synthesis of the title compounds is described that employs an enantioselective oxidative C-C bond formation catalyzed by berberine bridge enzyme (BBE) in the asymmetric key step. This unique reaction yielded enantiomerically pure (R)-benzylisoquinoline derivatives and (S)-berbines such as the natural product (S)-scoulerine, a sedative and muscle relaxing agent. The racemic substrates rac-1 required for the biotransformation were prepared in 4-8 linear steps using either a Bischler-Napieralski cyclization or a C1-Cα alkylation approach. The chemoenzymatic synthesis was applied to the preparation of fourteen enantiomerically pure alkaloids, including the natural products (S)-scoulerine and (R)-reticuline, and gave overall yields of up to 20% over 5-9 linear steps.

  19. Biocatalytic Organic Synthesis of Optically Pure (S)-Scoulerine and Berbine and Benzylisoquinoline Alkaloids

    Science.gov (United States)

    2011-01-01

    A chemoenzymatic approach for the asymmetric total synthesis of the title compounds is described that employs an enantioselective oxidative C–C bond formation catalyzed by berberine bridge enzyme (BBE) in the asymmetric key step. This unique reaction yielded enantiomerically pure (R)-benzylisoquinoline derivatives and (S)-berbines such as the natural product (S)-scoulerine, a sedative and muscle relaxing agent. The racemic substrates rac-1 required for the biotransformation were prepared in 4–8 linear steps using either a Bischler–Napieralski cyclization or a C1–Cα alkylation approach. The chemoenzymatic synthesis was applied to the preparation of fourteen enantiomerically pure alkaloids, including the natural products (S)-scoulerine and (R)-reticuline, and gave overall yields of up to 20% over 5–9 linear steps. PMID:21739961

  20. Ethylene in Organic Synthesis. Repetitive Hydrovinylation of Alkenes for Highly Enantioselective Syntheses of Pseudopterosins

    Science.gov (United States)

    Mans, Daniel J.; Cox, G. Adam; RajanBabu, T. V.

    2011-01-01

    In this report we highlight the significant potential of ethylene as a reagent for the introduction of a vinyl group with excellent stereoselectivity at three different stages in the synthesis of a broad class of natural products, best exemplified by syntheses of pseudopterosins. The late-stage applications of the asymmetric hydrovinylation reaction further illustrate the compatibility of the catalyst with complex functional groups. We also show that depending on the choice of the catalyst, it is possible to either enhance or even completely reverse the inherent diastereoselectivity in the reactions of advanced chiral intermediates. This should enable the synthesis of diastereomeric analogs of several classes of medicinally relevant compounds that are not readily accessible by the existing methods, which depend on ‘substrate-control’ for the installation of many of the chiral centers, especially in molecules of this class. PMID:21449569

  1. Flow through reactors for organic chemistry: directly electrically heated tubular mini reactors as an enabling technology for organic synthesis

    Directory of Open Access Journals (Sweden)

    Ulrich Kunz

    2009-11-01

    Full Text Available Until recently traditional heating in organic chemistry has been done with oil heating baths or using electric heat exchangers. With the advent of microwave equipment, heating by microwaves was rapidly introduced as standard method in organic chemistry laboratories, mainly because of the convenient possibility to operate at high temperature accompanied by accelerated reaction rates. In the present contribution we discuss the method of heating small, continuously operated reactors by passing electric current directly through the reactor wall as an enabling technology in organic chemistry. The benefit of this method is that the heat is generated directly inside the reactor wall. By this means high heating rates comparable to microwave ovens can be reached but at much lower cost for the equipment. A tool for the comparison of microwave heating and traditional heating is provided. As an example kinetic data for the acid catalyzed hydrolysis of methyl formate were measured using this heating concept. The reaction is not only a suitable model but also one of industrial importance since this is the main production process for formic acid.

  2. Flow through reactors for organic chemistry: directly electrically heated tubular mini reactors as an enabling technology for organic synthesis.

    Science.gov (United States)

    Kunz, Ulrich; Turek, Thomas

    2009-11-30

    Until recently traditional heating in organic chemistry has been done with oil heating baths or using electric heat exchangers. With the advent of microwave equipment, heating by microwaves was rapidly introduced as standard method in organic chemistry laboratories, mainly because of the convenient possibility to operate at high temperature accompanied by accelerated reaction rates. In the present contribution we discuss the method of heating small, continuously operated reactors by passing electric current directly through the reactor wall as an enabling technology in organic chemistry. The benefit of this method is that the heat is generated directly inside the reactor wall. By this means high heating rates comparable to microwave ovens can be reached but at much lower cost for the equipment. A tool for the comparison of microwave heating and traditional heating is provided. As an example kinetic data for the acid catalyzed hydrolysis of methyl formate were measured using this heating concept. The reaction is not only a suitable model but also one of industrial importance since this is the main production process for formic acid.

  3. Flow through reactors for organic chemistry: directly electrically heated tubular mini reactors as an enabling technology for organic synthesis

    Science.gov (United States)

    Turek, Thomas

    2009-01-01

    Summary Until recently traditional heating in organic chemistry has been done with oil heating baths or using electric heat exchangers. With the advent of microwave equipment, heating by microwaves was rapidly introduced as standard method in organic chemistry laboratories, mainly because of the convenient possibility to operate at high temperature accompanied by accelerated reaction rates. In the present contribution we discuss the method of heating small, continuously operated reactors by passing electric current directly through the reactor wall as an enabling technology in organic chemistry. The benefit of this method is that the heat is generated directly inside the reactor wall. By this means high heating rates comparable to microwave ovens can be reached but at much lower cost for the equipment. A tool for the comparison of microwave heating and traditional heating is provided. As an example kinetic data for the acid catalyzed hydrolysis of methyl formate were measured using this heating concept. The reaction is not only a suitable model but also one of industrial importance since this is the main production process for formic acid. PMID:20300506

  4. Genetically Modified Organism Trade Route and Biosafety-Is It a Failing Synthesis?

    OpenAIRE

    Debdatta Dobe; Rohini Sen

    2009-01-01

    Problem statement: GM regulations have spawned international conflicting reactions especially between US and EU, with countries requiring food aid caught midway. This article covers the following issues: Whether biotechnology policies of other countries affect the developing countries trade in agricultural crops? Does unregulated GM expansion and contamination, render the system fallacious? Can there be synthesis between trade and environment? Approach: This article also explores long term ef...

  5. The sulfamate functional group as a new anchor for solid-phase organic synthesis

    Science.gov (United States)

    Ciobanu; Maltais; Poirier

    2000-02-24

    [reaction: see text] Sulfamate derivatives were loaded on trityl chloride resin, and two variants of cleavage were developed for this sulfamate anchor: an acid treatment to easily restore the free sulfamate and a nucleophilic treatment to generate the corresponding phenol. In addition to loading/cleavage assays and stability experiments, a model sequence of reactions was performed with the new sulfamate anchor to show its applicability in further combinatorial solid-phase synthesis of libraries of biologically relevant sulfamate derivatives.

  6. Synthesis of cyclobutane lignans via an organic single electron oxidant–electron relay system†

    Science.gov (United States)

    Riener, Michelle; Nicewicz, David A.

    2013-01-01

    A direct method to synthesize lignan cyclobutanes and analogs via photoinduced electron transfer is presented. A variety of oxygenated alkenes are employed to furnish terminal or substituted cyclobutane adducts with complete regiocontrol, yielding cycloadducts with trans stereochemistry. Key to minimizing competing cycloreversion is the inclusion of an aromatic electron relay (ER). This method has been adapted to the synthesis of the natural products magnosalin and pellucidin A. PMID:24349680

  7. Exploiting Poly(ethylene glycol as a Matrix for Liquid-Phase Organic Synthesis

    Directory of Open Access Journals (Sweden)

    Kim D. Janda

    2000-08-01

    Full Text Available Soluble polymer-supported chemistry is a technology that allows the blending of the benefits of polymer-supported synthesis and solution-phase chemistry. Herein, we describe our recent efforts in this area targeted at exploring the scope of poly(ethylene glycol (PEG as the matrix. Specifically we describe the use of PEG as a support for triphenyl phosphine and for the Stille reaction.

  8. Chemical Priming of Plants Against Multiple Abiotic Stresses: Mission Possible?

    Science.gov (United States)

    Savvides, Andreas; Ali, Shawkat; Tester, Mark; Fotopoulos, Vasileios

    2016-04-01

    Crop plants are subjected to multiple abiotic stresses during their lifespan that greatly reduce productivity and threaten global food security. Recent research suggests that plants can be primed by chemical compounds to better tolerate different abiotic stresses. Chemical priming is a promising field in plant stress physiology and crop stress management. We review here promising chemical agents such as sodium nitroprusside, hydrogen peroxide, sodium hydrosulfide, melatonin, and polyamines that can potentially confer enhanced tolerance when plants are exposed to multiple abiotic stresses. The challenges and opportunities of chemical priming are addressed, with the aim to boost future research towards effective application in crop stress management.

  9. Recent Molecular Advances on Downstream Plant Responses to Abiotic Stress

    Directory of Open Access Journals (Sweden)

    Cláudia Regina Batista de Souza

    2012-07-01

    Full Text Available Abiotic stresses such as extremes of temperature and pH, high salinity and drought, comprise some of the major factors causing extensive losses to crop production worldwide. Understanding how plants respond and adapt at cellular and molecular levels to continuous environmental changes is a pre-requisite for the generation of resistant or tolerant plants to abiotic stresses. In this review we aimed to present the recent advances on mechanisms of downstream plant responses to abiotic stresses and the use of stress-related genes in the development of genetically engineered crops.

  10. Chemical Priming of Plants Against Multiple Abiotic Stresses: Mission Possible?

    Science.gov (United States)

    Savvides, Andreas; Ali, Shawkat; Tester, Mark; Fotopoulos, Vasileios

    2016-04-01

    Crop plants are subjected to multiple abiotic stresses during their lifespan that greatly reduce productivity and threaten global food security. Recent research suggests that plants can be primed by chemical compounds to better tolerate different abiotic stresses. Chemical priming is a promising field in plant stress physiology and crop stress management. We review here promising chemical agents such as sodium nitroprusside, hydrogen peroxide, sodium hydrosulfide, melatonin, and polyamines that can potentially confer enhanced tolerance when plants are exposed to multiple abiotic stresses. The challenges and opportunities of chemical priming are addressed, with the aim to boost future research towards effective application in crop stress management. PMID:26704665

  11. Depletion of abiotic resources in the steel production in Poland

    Directory of Open Access Journals (Sweden)

    D. Burchart-Korol

    2016-07-01

    Full Text Available Steelmaking processes consume a lot of energy and materials, therefore researchers are constantly looking for new ways of reducing the consumption of resources in the production processes. The main purpose of the article is to present abiotic resource depletion the in steel production in the case of integrated steelmaking route in Poland and its role in life cycle assessment. There are different methods of life cycle assessment for abiotic resources, the use of which affects the quality of the obtained information. The article presents some results of life cycle assessment of abiotic depletion.

  12. Chemical Priming of Plants Against Multiple Abiotic Stresses: Mission Possible?

    KAUST Repository

    Savvides, Andreas

    2015-12-15

    Crop plants are subjected to multiple abiotic stresses during their lifespan that greatly reduce productivity and threaten global food security. Recent research suggests that plants can be primed by chemical compounds to better tolerate different abiotic stresses. Chemical priming is a promising field in plant stress physiology and crop stress management. We review here promising chemical agents such as sodium nitroprusside, hydrogen peroxide, sodium hydrosulfide, melatonin, and polyamines that can potentially confer enhanced tolerance when plants are exposed to multiple abiotic stresses. The challenges and opportunities of chemical priming are addressed, with the aim to boost future research towards effective application in crop stress management.

  13. Daily variation of zooplankton abundance and evenness in the Rosana reservoir, Brazil: biotic and abiotic inferences

    Directory of Open Access Journals (Sweden)

    Érica M. Takahashi

    2014-03-01

    Full Text Available The zooplankton community presents stochastic temporal fluctuation and heterogeneous spatial variation determined by the relationships among the organisms and environmental conditions. We predicted that the temporal and spatial zooplankton distribution is heterogeneous and discrete, respectively, and that the daily variation of most abundant species is related to environmental conditions, specifically the availability of resources. Zooplankton samples were collected daily at three sampling stations in a lateral arm of the Rosana Reservoir (SP/PR. The zooplankton did not present significant differences in abundance and evenness among sampling stations, but the temporal variation of these attributes was significant. Abiotic variables and algal resource availability have significantly explained the daily variation of the most abundant species (p<0.001, however, the species distribution makes inferences on biotic relationships between them. Thus, not only the food resource availability is influential on the abundance of principal zooplankton species, but rather a set of factors (abiotic variables and biotic relationships.

  14. Evolution and Adaptation of Wild Emmer Wheat Populations to Biotic and Abiotic Stresses.

    Science.gov (United States)

    Huang, Lin; Raats, Dina; Sela, Hanan; Klymiuk, Valentina; Lidzbarsky, Gabriel; Feng, Lihua; Krugman, Tamar; Fahima, Tzion

    2016-08-01

    The genetic bottlenecks associated with plant domestication and subsequent selection in man-made agroecosystems have limited the genetic diversity of modern crops and increased their vulnerability to environmental stresses. Wild emmer wheat, the tetraploid progenitor of domesticated wheat, distributed along a wide range of ecogeographical conditions in the Fertile Crescent, has valuable "left behind" adaptive diversity to multiple diseases and environmental stresses. The biotic and abiotic stress responses are conferred by series of genes and quantitative trait loci (QTLs) that control complex resistance pathways. The study of genetic diversity, genomic organization, expression profiles, protein structure and function of biotic and abiotic stress-resistance genes, and QTLs could shed light on the evolutionary history and adaptation mechanisms of wild emmer populations for their natural habitats. The continuous evolution and adaptation of wild emmer to the changing environment provide novel solutions that can contribute to safeguarding food for the rapidly growing human population. PMID:27296141

  15. Evolution and Adaptation of Wild Emmer Wheat Populations to Biotic and Abiotic Stresses.

    Science.gov (United States)

    Huang, Lin; Raats, Dina; Sela, Hanan; Klymiuk, Valentina; Lidzbarsky, Gabriel; Feng, Lihua; Krugman, Tamar; Fahima, Tzion

    2016-08-01

    The genetic bottlenecks associated with plant domestication and subsequent selection in man-made agroecosystems have limited the genetic diversity of modern crops and increased their vulnerability to environmental stresses. Wild emmer wheat, the tetraploid progenitor of domesticated wheat, distributed along a wide range of ecogeographical conditions in the Fertile Crescent, has valuable "left behind" adaptive diversity to multiple diseases and environmental stresses. The biotic and abiotic stress responses are conferred by series of genes and quantitative trait loci (QTLs) that control complex resistance pathways. The study of genetic diversity, genomic organization, expression profiles, protein structure and function of biotic and abiotic stress-resistance genes, and QTLs could shed light on the evolutionary history and adaptation mechanisms of wild emmer populations for their natural habitats. The continuous evolution and adaptation of wild emmer to the changing environment provide novel solutions that can contribute to safeguarding food for the rapidly growing human population.

  16. Knowledge synthesis: Animal health and welfare in organic pig production - Final Report COREPIG

    OpenAIRE

    Früh, Barbara; Bochicchio, David; Edwards, Sandra; Hegelund, Lene; Leeb, Christine; Heinonen, Mari; Maupertuis, F.; Werne, Steffen; Wiberg, Sophia; Mejer, Helena; PRUNIER, Armelle; Roepstorff, Allan; Lubac, Stanislas; Bonde, Marianne; Rousing, Tine

    2011-01-01

    This report reviews the available information on the welfare of pigs when maintained according to organic standards in Europe. It begins by overviewing the populations of organic pigs in different countries at the time of writing (2007), the organic standards which govern their management and the systems in which they are typically kept. It then reviews for each stage in the production cycle (sows, suckling piglets, weaned pigs and fattening pigs) the available literature on health and welfar...

  17. How to prevent dimerization of laser dyes in water? Simulation and organic synthesis

    International Nuclear Information System (INIS)

    Xanthenes are widely used as laser dyes in ethanol medium because their photophysical properties there are excellent. On the other hand, when they are dissolved in water, their fluorescence is almost zero on account of the dimerization phenomenon (aggregation of two molecules) which is specific in water although the interaction between the two molecules (these dyes are mainly cations) be repulsive. The first part of this work deals with the dimerization study of two dyes, the 6G rhodamine and the 6G pyronine. Molecular dynamics simulation results (AMBER software) have been compared with those of the NMR; thus it has been possible to describe the geometry of the 6G rhodamine dimer and to identify two structures present in equal quantities for the 6G pyronine dimer. It has been demonstrated that the role of water is essential in the aggregation mechanism; this role can be understood as resulting of the hydrophobic effect. The second part of this work concerns the synthesis of rhodamines which are soluble but not able to dimerize in water at the running concentrations of the laser dyes. At first, aminophenol precursors having hydrophilic ionic groups on modifiable sites have been synthesized without changing their photophysical properties. The synthesis sequence of the 3-(2-alkylamino-4-hydroxyphenyl)propionic acids has not given the waited products but N-(3'-hydroxyphenyl)amino-alkylsulfonic acids have been obtained. Their condensation with the phthalic anhydride has led to dyes of a charge -2 at a pH of 5 in water and which have photophysical properties similar to those of the rhodamine 575 in ethanol and laser emission properties in the emission spectral range of the rhodamine 6G in ethanol. This synthesis work has then led to the preparation of two laser dyes usable in water. (author)

  18. Synthesis, Processing, and Characterization of Inorganic-Organic Hybrid Cross-Linked Silica, Organic Polyimide, and Inorganic Aluminosilicate Aerogels

    Science.gov (United States)

    Nguyen, Baochau N.; Guo, Haiquan N.; McCorkle, Linda S.

    2014-01-01

    As aerospace applications become ever more demanding, novel insulation materials with lower thermal conductivity, lighter weight and higher use temperature are required to fit the aerospace application needs. Having nanopores and high porosity, aerogels are superior thermal insulators, among other things. The use of silica aerogels in general is quite restricted due to their inherent fragility, hygroscopic nature, and poor mechanical properties, especially in extereme aerospace environments. Our research goal is to develop aerogels with better mechanical and environmental stability for a variety of aeronautic and space applications including space suit insulation for planetary surface missions, insulation for inflatable structures for habitats, inflatable aerodynamic decelerators for entry, descent and landing (EDL) operations, and cryotank insulation for advance space propulsion systems. Different type of aerogels including organic-inorganic polymer reinforced (hybrid) silica-based aerogels, polyimide aerogels and inorganic aluminosilicate aerogels have been developed and examined.

  19. Synthesis of magnetic nanoporous carbon from metal-organic framework for the fast removal of organic dye from aqueous solution

    Science.gov (United States)

    Jiao, Caina; Wang, Yanen; Li, Menghua; Wu, Qiuhua; Wang, Chun; Wang, Zhi

    2016-06-01

    In this paper, a magnetic nanoporous carbon (Fe3O4/NPC) was successfully synthesized by using MOF-5 as carbon precursor and Fe salt as magnetic precursor. The texture properties of the as-synthesized nanocomposite were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), vibration sample magnetometer (VSM), and N2 adsorption-desorption isotherms. The Fe3O4/NPC had a high surface area with strong magnetic strength. Its adsorption behavior was tested by its adsorption capacity for the removal of methylene blue from aqueous solution. The results demonstrated that the Fe3O4/NPC had a high adsorption capacity, rapid adsorption rate, and easy magnetic separabilty. Moreover, the adsorbent could be easily regenerated by washing it with ethanol. The Fe3O4/NPC can be used as a good alternative for the effective removal of organic dyes from wastewater.

  20. Direct and post-synthesis incorporation of chiral metallosalen catalysts into metal-organic frameworks for asymmetric organic transformations.

    Science.gov (United States)

    Xi, Weiqin; Liu, Yan; Xia, Qingchun; Li, Zijian; Cui, Yong

    2015-09-01

    Two chiral porous metal-organic frameworks (MOFs) were constructed from [VO(salen)]-derived dicarboxylate and dipyridine bridging ligands. After oxidation of V(IV) to V(V) , they were found to be highly effective, recyclable, and reusable heterogeneous catalysts for the asymmetric cyanosilylation of aldehydes with up to 95 % ee. Solvent-assisted linker exchange (SALE) treatment of the pillared-layer MOF with [Cr(salen)Cl]- or [Al(salen)Cl]-derived dipyridine ligands led to the formation of mixed-linker metallosalen-based frameworks and incorporation of [Cr(salen)] enabled its use as a heterogeneous catalyst in the asymmetric epoxide ring-opening reaction.

  1. Structural organization of films based on polyaniline/polysulfonic acid complexes depending on the synthesis method

    International Nuclear Information System (INIS)

    The optical properties and morphology of complexes based on polyaniline (PANI) and poly(2-acrylamido-2-methyl-1-propanesulfonic acid) (PAMPS), depending on their synthesis conditions, have been characterized by UV-visible spectroscopy and atomic force microscopy. The dependence of the electron absorption spectra of PANI/PAMPS complexes and the surface topography of their films on the initiation way of PANI formation (chemical and enzymatic) and the use of promoters of aniline polymerization has been investigated. The aniline polymerization kinetics with and without polymerization promoters has been studied. All PANI/PAMPS complexes are found to have a nanocomposite time-stable structure.

  2. Electrochemical Synthesis of a Microporous Conductive Polymer Based on a Metal-Organic Framework Thin Film

    KAUST Repository

    Lu, Chunjing

    2014-05-22

    A new approach to preparing 3D microporous conductive polymer has been demonstrated in the electrochemical synthesis of a porous polyaniline network with the utilization of a MOF thin film supported on a conducting substrate. The prepared porous polyaniline with well-defined uniform micropores of 0.84 nm exhibits a high BET surface area of 986 m2 g−1 and a high electric conductivity of 0.125 S cm−1 when doped with I2, which is superior to existing porous conducting materials of porous MOFs, CMPs, and COFs.

  3. The Abiotic Depletion Potential: Background, Updates, and Future

    Directory of Open Access Journals (Sweden)

    Lauran van Oers

    2016-03-01

    Full Text Available Depletion of abiotic resources is a much disputed impact category in life cycle assessment (LCA. The reason is that the problem can be defined in different ways. Furthermore, within a specified problem definition, many choices can still be made regarding which parameters to include in the characterization model and which data to use. This article gives an overview of the problem definition and the choices that have been made when defining the abiotic depletion potentials (ADPs for a characterization model for abiotic resource depletion in LCA. Updates of the ADPs since 2002 are also briefly discussed. Finally, some possible new developments of the impact category of abiotic resource depletion are suggested, such as redefining the depletion problem as a dilution problem. This means taking the reserves in the environment and the economy into account in the reserve parameter and using leakage from the economy, instead of extraction rate, as a dilution parameter.

  4. Circadian regulation of abiotic stress tolerance in plants.

    Science.gov (United States)

    Grundy, Jack; Stoker, Claire; Carré, Isabelle A

    2015-01-01

    Extremes of temperatures, drought and salinity cause widespread crop losses throughout the world and impose severe limitations on the amount of land that can be used for agricultural purposes. Hence, there is an urgent need to develop crops that perform better under such abiotic stress conditions. Here, we discuss intriguing, recent evidence that circadian clock contributes to plants' ability to tolerate different types of environmental stress, and to acclimate to them. The clock controls expression of a large fraction of abiotic stress-responsive genes, as well as biosynthesis and signaling downstream of stress response hormones. Conversely, abiotic stress results in altered expression and differential splicing of the clock genes, leading to altered oscillations of downstream stress-response pathways. We propose a range of mechanisms by which this intimate coupling between the circadian clock and environmental stress-response pathways may contribute to plant growth and survival under abiotic stress.

  5. Baseline inventory data users guide to abiotic GIS layers

    Data.gov (United States)

    US Fish and Wildlife Service, Department of the Interior — The Baseline Inventory Team was chartered by the Fulfilling the Promises Implementation Team to recommend minimum abiotic and biotic inventories for the National...

  6. Organization and expression of the Co1D-CA23 plasmid genes associated with colicin synthesis

    International Nuclear Information System (INIS)

    The authors have investigated the organization and regulation of the functioning of colicin genes, the immunity protein, and lysis protein of the colicinogenic plasmid Co1D-CA23. In addition they have analyzed the polypeptides synthesized in minicells carrying plasmid Co1D, its Th5 mutants, and the recombinant plasmids obtained on cloning of the EcoRV fragments of Co1D on vector BR325. They have determined the position of the promoter of the colicin gene and the direction of its transcription. Furthermore they were able to show that the gene determining cell immunity to colicin D is transcribed independently of the colicin gene from its own SOS-independent promoter. Treatment of the cells carrying plasmid Co1D with mitomycin C leads to the induction of synthesis of not only colicin but also of a protein with a molecular weight of 10 kdalton, causing under these conditions the death and lysis of the cells. Together with colicin, this protein is detected in the culture liquid on lysis of the cells. Plasmid mutations impairing the synthesis of the lysis protein inhibit the release of colicin into the medium. They have shown that the genes of colicin and the lysis protein are arranged into one operon, the lysis gene being transcribed after the colicin gene. They have proposed a genetic map for plasmid Co1D-CA23

  7. Mild Conditions for Deuteration of Primary and Secondary Arylamines for the Synthesis of Deuterated Optoelectronic Organic Molecules

    Directory of Open Access Journals (Sweden)

    Anwen M. Krause-Heuer

    2014-11-01

    Full Text Available Deuterated arylamines demonstrate great potential for use in optoelectronic devices, but their widespread utility requires a method for large-scale synthesis. The incorporation of these deuterated materials into optoelectronic devices also provides the opportunity for studies of the functioning device using neutron reflectometry based on the difference in the scattering length density between protonated and deuterated compounds. Here we report mild deuteration conditions utilising standard laboratory glassware for the deuteration of: diphenylamine, N-phenylnaphthylamine, N-phenyl-o-phenylenediamine and 1-naphthylamine (via H/D exchange in D2O at 80 °C, catalysed by Pt/C and Pd/C. These conditions were not successful in the deuteration of triphenylamine or N,N-dimethylaniline, suggesting that these mild conditions are not suitable for the deuteration of tertiary arylamines, but are likely to be applicable for the deuteration of other primary and secondary arylamines. The deuterated arylamines can then be used for synthesis of larger organic molecules or polymers with optoelectronic applications.

  8. Organic Materials in the Undergraduate Laboratory: Microscale Synthesis and Investigation of a Donor-Acceptor Molecule

    Science.gov (United States)

    Pappenfus, Ted M.; Schliep, Karl B.; Dissanayake, Anudaththa; Ludden, Trevor; Nieto-Ortega, Belen; Lopez Navarrete, Juan T.; Ruiz Delgado, M. Carmen; Casado, Juan

    2012-01-01

    A series of experiments for undergraduate courses (e.g., organic, physical) have been developed in the area of small molecule organic materials. These experiments focus on understanding the electronic and redox properties of a donor-acceptor molecule that is prepared in a convenient one-step microscale reaction. The resulting intensely colored…

  9. Mitigating abiotic stress in crop plants by microorganisms

    OpenAIRE

    Milošević Nada A.; Marinković Jelena B.; Tintor Branislava B.

    2012-01-01

    Microorganisms could play an important role in adaptation strategies and increase of tolerance to abiotic stresses in agricultural plants. Plant-growth-promoting rhizobacteria (PGPR) mitigate most effectively the impact of abiotic stresses (drought, low temperature, salinity, metal toxicity, and high temperatures) on plants through the production of exopolysaccharates and biofilm formation. PGPR mitigate the impact of drought on plants through a process so-called induced systemic tolera...

  10. Genetic improvement of rice for biotic and abiotic stress tolerance

    OpenAIRE

    ANSARI, MAHMOOD UR RAHMAN; Shaheen, Tayyaba; BUKHARI, SHAZAI; Husnain, Tayyab

    2015-01-01

    Rice (Oryza sativa L.) is among the most important food crops that provide a staple food for nearly half of the world's population. Rice crops are prone to various types of stresses, both biotic and abiotic. Biotic stresses include insect pests, fungus, bacteria, viruses, and herbicide toxicity. Among abiotic stresses, drought, cold, and salinity are also well studied in rice. Various genes have been identified, cloned, and characterized to combat these stresses and protect rice crops. T...

  11. Abiotic and microbial interactions during anaerobic transformations of Fe(II and NOx-

    Directory of Open Access Journals (Sweden)

    Flynn ePicardal

    2012-03-01

    Full Text Available Microbial Fe(II oxidation using NO3- as the terminal electron acceptor (nitrate-dependent Fe(II oxidation; NDFO has been studied for over 15 years. Although there are reports of autotrophic isolates and stable enrichments, many of the bacteria capable of NDFO are known organotrophic NO3- -reducers that require the presence of an organic, primary substrate, e.g., acetate, for significant amounts of Fe(II oxidation. Although the thermodynamics of Fe(II oxidation are favorable when coupled to either NO3- or NO2- reduction, the kinetics of abiotic Fe(II oxidation by NO3- are relatively slow except under special conditions. NDFO is typically studied in batch cultures containing millimolar concentrations of Fe(II, NO3-, and the primary substrate. In such systems, NO2- is often observed to accumulate in culture media during Fe(II oxidation. Compared to NO3-, abiotic reactions of biogenic NO2- and Fe(II are relatively rapid. The kinetics and reaction pathways of Fe(II oxidation by NO2- are strongly affected by medium composition and pH, reactant concentration, and the presence of Fe(II-sorptive surfaces, e.g., Fe(III oxyhydroxides and cellular surfaces. In batch cultures, the combination of abiotic and microbial Fe(II oxidation can alter product distribution and, more importantly, results in the formation of intracellular precipitates and extracellular Fe(III oxyhydroxide encrustations that apparently limit further cell growth and Fe(II oxidation. Unless steps are taken to minimize or account for potential abiotic reactions, results of microbial NDFO studies can be obfuscated by artifacts of the chosen experimental conditions, the use of inappropriate analytical methods, and the resulting uncertainties about the relative importance of abiotic and microbial reactions.In this manuscript, abiotic reactions of NO3- and NO2- with aqueous Fe2+, chelated Fe(II, and solid-phase Fe(II are reviewed along with factors that can influence overall NDFO reac

  12. Synthesis and characterization of [BMIM]bromide using microwave-assisted organic synthesis method and its application for dissolution of palm empty fruit bunch

    International Nuclear Information System (INIS)

    The decrease of cellulose crystallinity index of palm empty fruit bunch is crucial for the next application of cellulose as raw material for various biofuel and its derivatives. The aim of this research is to decrease the cellulose crystallinity index of palm empty fruit bunch using 1-butyl-3-methylimidazoliumbromide or [BMIM] bromide which has been synthesized using Microwave-Assisted Organic Synthesis (MAOS) method. Conventional reaction method has also been carried out to synthesize [BMIM]bromide for comparison as well. The characterization of synthesized product using FTIR, 1H-NMR, 13C-NMR and LC-MS showed that these reactions have been carried out successfully. The results showed that MAOS method is up to 90% faster in producing [BMIM]bromide compare to the conventional method. The application of [BMIM]bromide for dissolution of palm empty fruit bunch showed that cellulose and lignin could be extracted using stirring process for 20 hours. The decrease of cellulose crystallinity index and its morphology changes were identified using FTIR and Scanning Electron Microscope

  13. Synthesis and characterization of [BMIM]bromide using microwave-assisted organic synthesis method and its application for dissolution of palm empty fruit bunch

    Energy Technology Data Exchange (ETDEWEB)

    Arianie, Lucy, E-mail: lucy205@yahoo.com [Department of Chemistry, Faculty of Mathematics and Natural Science, Universitas Tanjungpura, Jl. A.Yani, 73 Pontianak 78124 (Indonesia); Wahyuningrum, Deana, E-mail: deana@chem.itb.ac.id; Nurrachman, Zeily, E-mail: deana@chem.itb.ac.id; Natalia, Dessy, E-mail: deana@chem.itb.ac.id [Department of Chemistry, Faculty of Mathematics and Natural Science, Institut Teknologi Bandung, Jl. Ganesha 10 Bandung 40132 (Indonesia)

    2014-03-24

    The decrease of cellulose crystallinity index of palm empty fruit bunch is crucial for the next application of cellulose as raw material for various biofuel and its derivatives. The aim of this research is to decrease the cellulose crystallinity index of palm empty fruit bunch using 1-butyl-3-methylimidazoliumbromide or [BMIM] bromide which has been synthesized using Microwave-Assisted Organic Synthesis (MAOS) method. Conventional reaction method has also been carried out to synthesize [BMIM]bromide for comparison as well. The characterization of synthesized product using FTIR, {sup 1}H-NMR, {sup 13}C-NMR and LC-MS showed that these reactions have been carried out successfully. The results showed that MAOS method is up to 90% faster in producing [BMIM]bromide compare to the conventional method. The application of [BMIM]bromide for dissolution of palm empty fruit bunch showed that cellulose and lignin could be extracted using stirring process for 20 hours. The decrease of cellulose crystallinity index and its morphology changes were identified using FTIR and Scanning Electron Microscope.

  14. Synthesis of a Two-Dimensional Covalent Organic Monolayer through Dynamic Imine Chemistry at the Air/Water Interface.

    Science.gov (United States)

    Dai, Wenyang; Shao, Feng; Szczerbiński, Jacek; McCaffrey, Ryan; Zenobi, Renato; Jin, Yinghua; Schlüter, A Dieter; Zhang, Wei

    2016-01-01

    A two-dimensional covalent organic monolayer was synthesized from simple aromatic triamine and dialdehyde building blocks by dynamic imine chemistry at the air/water interface (Langmuir-Blodgett method). The obtained monolayer was characterized by optical microscopy, scanning electron microscopy, and atomic force microscopy, which unambiguously confirmed the formation of a large (millimeter range), unimolecularly thin aromatic polyimine sheet. The imine-linked chemical structure of the obtained monolayer was characterized by tip-enhanced Raman spectroscopy, and the peak assignment was supported by spectra simulated by density functional theory. Given the modular nature and broad substrate scope of imine formation, the work reported herein opens up many new possibilities for the synthesis of customizable 2D polymers and systematic studies of their structure-property relationships.

  15. Nanoparticle Cookies Derived from Metal-Organic Frameworks: Controlled Synthesis and Application in Anode Materials for Lithium-Ion Batteries.

    Science.gov (United States)

    Wang, Shuhai; Chen, Minqi; Xie, Yanyu; Fan, Yanan; Wang, Dawei; Jiang, Ji-Jun; Li, Yongguang; Grützmacher, Hansjörg; Su, Cheng-Yong

    2016-05-01

    The capacity of anode materials plays a critical role in the performance of lithium-ion batteries. Using the nanocrystals of oxygen-free metal-organic framework ZIF-67 as precursor, a one-step calcination approach toward the controlled synthesis of CoO nanoparticle cookies with excellent anodic performances is developed in this work. The CoO nanoparticle cookies feature highly porous structure composed of small CoO nanoparticles (≈12 nm in diameter) and nitrogen-rich graphitic carbon matrix (≈18 at% in nitrogen content). Benefiting from such unique structure, the CoO nanoparticle cookies are capable of delivering superior specific capacity and cycling stability (1383 mA h g(-1) after 200 runs at 100 mA g(-1) ) over those of CoO and graphite.

  16. Synthesis of an extra-large molecular sieve using proton sponges as organic structure-directing agents

    Science.gov (United States)

    Martínez-Franco, Raquel; Moliner, Manuel; Yun, Yifeng; Sun, Junliang; Wan, Wei; Zou, Xiaodong; Corma, Avelino

    2013-01-01

    The synthesis of crystalline microporous materials containing large pores is in high demand by industry, especially for the use of these materials as catalysts in chemical processes involving bulky molecules. An extra-large–pore silicoaluminophosphate with 16-ring openings, ITQ-51, has been synthesized by the use of bulky aromatic proton sponges as organic structure-directing agents. Proton sponges show exceptional properties for directing extra-large zeolites because of their unusually high basicity combined with their large size and rigidity. This extra-large–pore material is stable after calcination, being one of the very few examples of hydrothermally stable molecular sieves containing extra-large pores. The structure of ITQ-51 was solved from submicrometer-sized crystals using the rotation electron diffraction method. Finally, several hypothetical zeolites related to ITQ-51 have been proposed. PMID:23431186

  17. Synthesis of five- and six-membered cyclic organic peroxides: Key transformations into peroxide ring-retaining products

    Directory of Open Access Journals (Sweden)

    Alexander O. Terent'ev

    2014-01-01

    Full Text Available The present review describes the current status of synthetic five and six-membered cyclic peroxides such as 1,2-dioxolanes, 1,2,4-trioxolanes (ozonides, 1,2-dioxanes, 1,2-dioxenes, 1,2,4-trioxanes, and 1,2,4,5-tetraoxanes. The literature from 2000 onwards is surveyed to provide an update on synthesis of cyclic peroxides. The indicated period of time is, on the whole, characterized by the development of new efficient and scale-up methods for the preparation of these cyclic compounds. It was shown that cyclic peroxides remain unchanged throughout the course of a wide range of fundamental organic reactions. Due to these properties, the molecular structures can be greatly modified to give peroxide ring-retaining products. The chemistry of cyclic peroxides has attracted considerable attention, because these compounds are used in medicine for the design of antimalarial, antihelminthic, and antitumor agents.

  18. Synthesis of five- and six-membered cyclic organic peroxides: Key transformations into peroxide ring-retaining products

    Science.gov (United States)

    Borisov, Dmitry A; Vil’, Vera A; Dembitsky, Valery M

    2014-01-01

    Summary The present review describes the current status of synthetic five and six-membered cyclic peroxides such as 1,2-dioxolanes, 1,2,4-trioxolanes (ozonides), 1,2-dioxanes, 1,2-dioxenes, 1,2,4-trioxanes, and 1,2,4,5-tetraoxanes. The literature from 2000 onwards is surveyed to provide an update on synthesis of cyclic peroxides. The indicated period of time is, on the whole, characterized by the development of new efficient and scale-up methods for the preparation of these cyclic compounds. It was shown that cyclic peroxides remain unchanged throughout the course of a wide range of fundamental organic reactions. Due to these properties, the molecular structures can be greatly modified to give peroxide ring-retaining products. The chemistry of cyclic peroxides has attracted considerable attention, because these compounds are used in medicine for the design of antimalarial, antihelminthic, and antitumor agents. PMID:24454562

  19. Synthesis of 5′-O-DMT-2′-O-TBS mononucleosides using an organic catalyst

    Science.gov (United States)

    Lee, Sunggi; Blaisdell, Thomas P.; Kasaplar, Pinar; Sun, Xixi

    2014-01-01

    This unit describes a highly effective method to produce 5′-O-DMT-2′-O-TBS mononucleosides selectively using a small organic catalyst. This methodology avoids the tedious protection/deprotection strategy necessary to differentiate the 2′- and 3′-hydroxyl groups in a ribonucleoside. The catalyst was synthesized in two steps starting from the condensation of valinol and cyclopentyl aldehyde, followed by anionic addition of N-methylimidazole. Ring closure of the amino alcohol with N,N-dimethylformamide dimethyl acetal in methanol furnishes the catalyst. All four 2′-O-TBS protected mono-nucleosides, U, ABz, GIb, and CAc, were produced in a single step using 10 to 20 mol% of the catalyst at room temperature with excellent yields and selectivity. Further transformation to phosphoramidite demonstrates the utility of this protocol toward the preparation of monomers useful for automated synthesis of RNA. PMID:24961720

  20. Isoreticular Series of (3,24)-Connected Metal-Organic Frameworks: Facile Synthesis and High Methane Uptake Properties

    Energy Technology Data Exchange (ETDEWEB)

    Barin, G; Krungleviciute, V; Gomez-Gualdron, DA; Sarjeant, AA; Snurr, RQ; Hupp, JT; Yildirim, T; Farha, OK

    2014-03-11

    We have successfully used a highly efficient copper-catalyzed "click" reaction for the synthesis of a new series of hexacarboxylic acid linkers with varying sizes for the construction of isoreticular (3,24)-connected metal-organic frameworks (MOFs)-namely, NU-138, NU-139, and NU-140. One of these MOFs, NU-140, exhibits a gravimetric methane uptake of 0.34 g/g at 65 bar and 298 K, corresponding to almost 70% of the DOE target (0.5 g/g), and has a working capacity (deliverable amount between 65 and 5 bar) of 0.29 g/g, which translates into a volumetric working capacity of 170 cc(STP)/cc. These values demonstrate that NU-140 performs well for methane storage purposes, from both a gravimetric and a volumetric point of view. Adsorption of CO2 and H-2 along with simulated isotherms are also reported.

  1. Synthesis and characterization of amine-functionalized mixed-ligand metal-organic frameworks of UiO-66 topology.

    Science.gov (United States)

    Chavan, Sachin M; Shearer, Greig C; Svelle, Stian; Olsbye, Unni; Bonino, Francesca; Ethiraj, Jayashree; Lillerud, Karl Petter; Bordiga, Silvia

    2014-09-15

    A series of amine-functionalized mixed-linker metal-organic frameworks (MOFs) of idealized structural formula Zr6O4(OH)4(BDC)(6-6X)(ABDC)6X (where BDC = benzene-1,4-dicarboxylic acid, ABDC = 2-aminobenzene-1,4-dicarboxylic acid) has been prepared by solvothermal synthesis. The materials have been characterized by thermogravimetric analysis (TGA), powder X-ray diffraction (PXRD), and Fourier transform infrared (FTIR) spectroscopy with the aim of elucidating the effect that varying the degrees of amine functionalization has on the stability (thermal and chemical) and porosity of the framework. This work includes the first application of ultraviolet-visible light (UV-vis) spectroscopy in the quantification of ABDC in mixed-linker MOFs.

  2. Synthesis and characterization of a helicene-based imidazolium salt and its application in organic molecular electronics.

    Science.gov (United States)

    Storch, Jan; Zadny, Jaroslav; Strasak, Tomas; Kubala, Martin; Sykora, Jan; Dusek, Michal; Cirkva, Vladimir; Matejka, Pavel; Krbal, Milos; Vacek, Jan

    2015-02-01

    Herein we demonstrate the synthesis of a helicene-based imidazolium salt. The salt was prepared by starting from racemic 2-methyl[6]helicene, which undergoes radical bromination to yield 2-(bromomethyl)[6]helicene. Subsequent treatment with 1-butylimidazole leads to the corresponding salt 1-butyl-3-(2-methyl[6]helicenyl)-imidazolium bromide. The prepared salt was subsequently characterized by using NMR spectroscopy and X-ray analysis, various optical spectrometric techniques, and computational chemistry tools. Finally, the imidazolium salt was immobilized onto a SiO2 substrate as a crystalline or amorphous deposit. The deposited layers were used for the development of organic molecular semiconductor devices and the construction of a fully reversible humidity sensor.

  3. Synthesis of five- and six-membered cyclic organic peroxides: Key transformations into peroxide ring-retaining products.

    Science.gov (United States)

    Terent'ev, Alexander O; Borisov, Dmitry A; Vil', Vera A; Dembitsky, Valery M

    2014-01-01

    The present review describes the current status of synthetic five and six-membered cyclic peroxides such as 1,2-dioxolanes, 1,2,4-trioxolanes (ozonides), 1,2-dioxanes, 1,2-dioxenes, 1,2,4-trioxanes, and 1,2,4,5-tetraoxanes. The literature from 2000 onwards is surveyed to provide an update on synthesis of cyclic peroxides. The indicated period of time is, on the whole, characterized by the development of new efficient and scale-up methods for the preparation of these cyclic compounds. It was shown that cyclic peroxides remain unchanged throughout the course of a wide range of fundamental organic reactions. Due to these properties, the molecular structures can be greatly modified to give peroxide ring-retaining products. The chemistry of cyclic peroxides has attracted considerable attention, because these compounds are used in medicine for the design of antimalarial, antihelminthic, and antitumor agents. PMID:24454562

  4. Synthesis and evaluation of new organic and phosphorous derivatives against ionizing radiation: study of the in vitro mechanism of action

    International Nuclear Information System (INIS)

    This work falls under a research program. The aim was to synthesize new organic phosphorylated compounds having an interesting radio pharmacological activity without toxicity. That is why, we carried out the synthesis of new benzothiazole and thiadiazole N-substituted derivatives as thiols, amino thiols, acids thio-sulfonic and phosphoro thioates. All these compounds were characterized by NMR (proton, carbon, phosphorus, 2D), by mass spectrometry, elementary analyzes and for some of them by diffraction of x-rays. The activity of the majority of them was evaluated by in vitro tests. The experimental results were confirmed by theoretical study: the aim of D.F.T. calculation was the study of the mechanism of capture of the free radicals by our compounds. In addition, a study of relation structure activity (Q.S.A.R.) was carried out. Our results allow us to create a model making it possible to establish structure-activity relationship. (author)

  5. Solvents in Organic Synthesis: Replacement and Multi-step Reaction Systems

    DEFF Research Database (Denmark)

    Gani, Rafiqul; Gómez, Paola Arenas; Folic, Milica;

    2008-01-01

    with the principles of green chemistry, highlight the need to minimize and optimize the use of organic solvents as much as possible. One important step in optimizing organic solvent use is the identification of suitable ‘greener' solvents that can help to minimize the environmental, health and safety concerns during...... design and commercial manufacture of chemical products. A method for selecting appropriate ‘greener' solvents for the promotion of a class of organic reactions has been previously developed by Gani et al. This method employs estimates of thermodynamic properties to generate a knowledge base of reaction...

  6. Italian Chemists’ Contributions to Named Reactions in Organic Synthesis: An Historical Perspective

    Directory of Open Access Journals (Sweden)

    Gianluca Papeo

    2013-09-01

    Full Text Available From the second half of the 19th century up to modern times, the tremendous contribution of Italian chemists to the development of science resulted in the discovery of a number of innovative chemical transformations. These reactions were subsequently christened according to their inventors’ name and so entered into the organic chemistry portfolio of “named organic reactions”. As these discoveries were being conceived, massive social, political and geographical changes in these chemists’ homeland were also occurring. In this review, a brief survey of known (and some lesser known named organic reactions discovered by Italian chemists, along with their historical contextualization, is presented.

  7. The design and synthesis of fused thiophenes and their applications in organic field-effect transistors

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    Fused thiophenes refer to oligothienoacenes in which several thiophenes are coupled together via twoor multi-positions and their derivatives. The synthesized organic semiconductors based on fused thiophenes exhibit excellent field effect properties due to their efficient intermolecular S…S interactions and π…π stacking. The performances of organic field-effect transistors (OFETs) depend not only on the materials but also on the devices. Such factors which influence the device performances as device structures, fabrication technologies and interface engineering are extensively investigated based on the fused thiophenes. Searching for new organic semiconductors and improving the device fabrication technologies are two major issues in the development of OFETs.

  8. Enzymatic Synthesis of Esculin Ester in Ionic Liquids Buffered with Organic Solvents

    DEFF Research Database (Denmark)

    Hu, Yifan; Guo, Zheng; Lue, Bena-Marie;

    2009-01-01

    The enzymatic esterification of esculin catalyzed by Candida antarctica lipase B (Novozym 435) was carried out in ionic liquid (IL)-organic solvent mixed systems in comparison with individual systems. The reaction behaviors in IL-organic solvents were systemically evaluated using acetone as a model...... solvent. With organic solvents as media, the esterification rates of esculin depended mainly on its solubility in solvents; for the reactions in ILs, the reaction rates were generally low, and the anion part of the IL played a critical role in enzyme activity. Therefore, the esterification of esculin......](-) > [MDEGSO(4)](-) > [OctSO(4)](-) > [ES](-) = [DMP](-) = [OTs](-) = CI-. The reaction behaviors differed in different systems and largely depended on the properties of the ILs and organic solvents. In general, improvements were observed in terms of both solubility and reaction efficiency. The knowledge...

  9. Synthesis of Metal-Organic Zeolites with Homochirality and High Porosity for Enantioselective Separation.

    Science.gov (United States)

    Xu, Zhong-Xuan; Liu, Liyang; Zhang, Jian

    2016-07-01

    Using lactic acid derivatives as chiral ligands, a pair of unprecedented homochiral metal-organic zeolites have been synthesized that feature zeotype CAN topology and have high porosity for enantioselective separation of racemates.

  10. Template-mediated Synthesis of Hollow Microporous Organic Nanorods with Tunable Aspect Ratio

    Science.gov (United States)

    Li, Qingyin; Jin, Shangbin; Tan, Bien

    2016-08-01

    Hollow microporous organic nanorods (HMORs) with hypercrosslinked polymer (HCPs) shells were synthesized through emulsion polymerization followed by hypercrosslinking. The HMORs have tunable aspect ratios, high BET surface areas and monodispersed morphologies, showing good performance in gas adsorpion.

  11. Synthesis, structure, and opto-electronic properties of organic-based nanoscale heterojunctions

    OpenAIRE

    Cimrová Vĕra; Rezek Bohuslav; Čermák Jan; Kromka Alexander; Ledinský Martin; Hubík Pavel; Mareš Jiří; Purkrt Adam; Fejfar Antonín; Kočka Jan

    2011-01-01

    Abstract Enormous research effort has been put into optimizing organic-based opto-electronic systems for efficient generation of free charge carriers. This optimization is mainly due to typically high dissociation energy (0.1-1 eV) and short diffusion length (10 nm) of excitons in organic materials. Inherently, interplay of microscopic structural, chemical, and opto-electronic properties plays crucial role. We show that employing and combining advanced scanning probe techniques can provide us...

  12. Homolytic substitution at phosphorus for C–P bond formation in organic synthesis

    Science.gov (United States)

    2013-01-01

    Summary Organophosphorus compounds are important in organic chemistry. This review article covers emerging, powerful synthetic approaches to organophosphorus compounds by homolytic substitution at phosphorus with a carbon-centered radical. Phosphination reagents include diphosphines, chalcogenophosphines and stannylphosphines, which bear a weak P–heteroatom bond for homolysis. This article deals with two transformations, radical phosphination by addition across unsaturated C–C bonds and substitution of organic halides. PMID:23843922

  13. Synthesis and optical features of an europium organic-inorganic silicate hybrid

    Energy Technology Data Exchange (ETDEWEB)

    Franville, A.C.; Zambon, D.; Mahiou, R.; Chou, S.; Cousseins, J.C. [Universite Blaise Pascal, Aubiere (France). Lab. des Materiaux Inorganiques; Troin, Y. [Laboratoire de Chimie des Heterocycles et des Glucides, EA 987, Universite Blaise-Pascal and ENSCCF, F-63177 Aubiere Cedex (France)

    1998-07-24

    A europium organic-inorganic silicate hybrid was synthesized by grafting a coordinative group (dipicolinic acid) to a silicate network precursor (3-aminopropyltriethoxysilane) via a covalent bonding. Sol-gel process and complexation were performed using different experimental conditions. The hybrid materials, in particular the Eu{sup 3+} coordination mode, were characterized by infrared and luminescence spectroscopies. Morphology of the materials and TG analysis showed that grafted silica enhanced thermal and mechanical resistances of the organic part. (orig.) 7 refs.

  14. Metabolomics as a Tool to Investigate Abiotic Stress Tolerance in Plants

    Directory of Open Access Journals (Sweden)

    Aurelio Gómez-Cadenas

    2013-03-01

    Full Text Available Metabolites reflect the integration of gene expression, protein interaction and other different regulatory processes and are therefore closer to the phenotype than mRNA transcripts or proteins alone. Amongst all –omics technologies, metabolomics is the most transversal and can be applied to different organisms with little or no modifications. It has been successfully applied to the study of molecular phenotypes of plants in response to abiotic stress in order to find particular patterns associated to stress tolerance. These studies have highlighted the essential involvement of primary metabolites: sugars, amino acids and Krebs cycle intermediates as direct markers of photosynthetic dysfunction as well as effectors of osmotic readjustment. On the contrary, secondary metabolites are more specific of genera and species and respond to particular stress conditions as antioxidants, Reactive Oxygen Species (ROS scavengers, coenzymes, UV and excess radiation screen and also as regulatory molecules. In addition, the induction of secondary metabolites by several abiotic stress conditions could also be an effective mechanism of cross-protection against biotic threats, providing a link between abiotic and biotic stress responses. Moreover, the presence/absence and relative accumulation of certain metabolites along with gene expression data provides accurate markers (mQTL or MWAS for tolerant crop selection in breeding programs.

  15. Screening for Abiotic Stress Tolerance in Rice: Salt, Cold, and Drought.

    Science.gov (United States)

    Almeida, Diego M; Almadanim, M Cecília; Lourenço, Tiago; Abreu, Isabel A; Saibo, Nelson J M; Oliveira, M Margarida

    2016-01-01

    Rice (Oryza sativa) is the primary source of food for more than half of the world population. Most rice varieties are severely injured by abiotic stresses, with strong social and economic impact. Understanding rice responses to stress may help breeding for more tolerant varieties. However, papers dealing with stress experiments often describe very different experimental designs, thus making comparisons difficult. The use of identical setups is the only way to generate comparable data. This chapter is organized into three sections, describing the experimental conditions established at the Genomics of Plant Stress (GPlantS) unit of ITQB to assess the response of rice plants to three different abiotic stresses--high salinity, cold stress, and drought. All sections include a detailed description of the materials and methodology, as well as useful notes gathered from the GPlantS team's experience. We use rice seedlings as plants at this stage show high sensitivity to abiotic stresses. For the salt and cold stress assays we use hydroponic cultures, while for the drought assay plants are grown in soil and subjected to water withholding. All setups enable visual score determination and are suitable for sample collection along the imposition of stress. The proposed methodologies are simple and affordable to implement in most labs, allowing the discrimination of several rice genotypes at the molecular and phenotypic level. PMID:26867623

  16. Hydrogen sulfide regulates abiotic stress tolerance and biotic stress resistance in Arabidopsis

    Institute of Scientific and Technical Information of China (English)

    Haitao Shi; Tiantian Ye; Ning Han; Hongwu Bian; Xiaodong Liu; Zhulong Chan

    2015-01-01

    Hydrogen sulfide (H2S) is an important gaseous molecule in various plant developmental processes and plant stress responses. In this study, the transgenic Arabidopsis thaliana plants with modulated expressions of two cysteine desulfhydrases, and exogenous H2S donor (sodium hydrosulfide, NaHS) and H2S scavenger (hypotaurine, HT) pre-treated plants were used to dissect the involvement of H2S in plant stress responses. The cysteine desulfhydrases overexpressing plants and NaHS pre-treated plants exhibited higher endogenous H2S level and improved abiotic stress tolerance and biotic stress resistance, while cysteine desulfhydrases knockdown plants and HT pre-treated plants displayed lower endogenous H2S level and decreased stress resistance. Moreover, H2S upregulated the transcripts of multiple abiotic and biotic stress-related genes, and inhibited reactive oxygen species (ROS) accumulation. Interest-ingly, MIR393-mediated auxin signaling including MIR393a/b and their target genes (TIR1, AFB1, AFB2, and AFB3) was transcrip-tional y regulated by H2S, and was related with H2S-induced antibacterial resistance. Moreover, H2S regulated 50 carbon metabolites including amino acids, organic acids, sugars, sugar alcohols, and aromatic amines. Taken together, these results indicated that cysteine desulfhydrase and H2S conferred abiotic stress tolerance and biotic stress resistance, via affecting the stress-related gene expressions, ROS metabolism, metabolic homeostasis, and MIR393-targeted auxin receptors.

  17. Hydrogen sulfide regulates abiotic stress tolerance and biotic stress resistance in Arabidopsis.

    Science.gov (United States)

    Shi, Haitao; Ye, Tiantian; Han, Ning; Bian, Hongwu; Liu, Xiaodong; Chan, Zhulong

    2015-07-01

    Hydrogen sulfide (H2S) is an important gaseous molecule in various plant developmental processes and plant stress responses. In this study, the transgenic Arabidopsis thaliana plants with modulated expressions of two cysteine desulfhydrases, and exogenous H2S donor (sodium hydrosulfide, NaHS) and H2S scavenger (hypotaurine, HT) pre-treated plants were used to dissect the involvement of H2S in plant stress responses. The cysteine desulfhydrases overexpressing plants and NaHS pre-treated plants exhibited higher endogenous H2S level and improved abiotic stress tolerance and biotic stress resistance, while cysteine desulfhydrases knockdown plants and HT pre-treated plants displayed lower endogenous H2S level and decreased stress resistance. Moreover, H2S upregulated the transcripts of multiple abiotic and biotic stress-related genes, and inhibited reactive oxygen species (ROS) accumulation. Interestingly, MIR393-mediated auxin signaling including MIR393a/b and their target genes (TIR1, AFB1, AFB2, and AFB3) was transcriptionally regulated by H2S, and was related with H2S-induced antibacterial resistance. Moreover, H2S regulated 50 carbon metabolites including amino acids, organic acids, sugars, sugar alcohols, and aromatic amines. Taken together, these results indicated that cysteine desulfhydrase and H2S conferred abiotic stress tolerance and biotic stress resistance, via affecting the stress-related gene expressions, ROS metabolism, metabolic homeostasis, and MIR393-targeted auxin receptors.

  18. Hydrogen sulfide regulates abiotic stress tolerance and biotic stress resistance in Arabidopsis.

    Science.gov (United States)

    Shi, Haitao; Ye, Tiantian; Han, Ning; Bian, Hongwu; Liu, Xiaodong; Chan, Zhulong

    2015-07-01

    Hydrogen sulfide (H2S) is an important gaseous molecule in various plant developmental processes and plant stress responses. In this study, the transgenic Arabidopsis thaliana plants with modulated expressions of two cysteine desulfhydrases, and exogenous H2S donor (sodium hydrosulfide, NaHS) and H2S scavenger (hypotaurine, HT) pre-treated plants were used to dissect the involvement of H2S in plant stress responses. The cysteine desulfhydrases overexpressing plants and NaHS pre-treated plants exhibited higher endogenous H2S level and improved abiotic stress tolerance and biotic stress resistance, while cysteine desulfhydrases knockdown plants and HT pre-treated plants displayed lower endogenous H2S level and decreased stress resistance. Moreover, H2S upregulated the transcripts of multiple abiotic and biotic stress-related genes, and inhibited reactive oxygen species (ROS) accumulation. Interestingly, MIR393-mediated auxin signaling including MIR393a/b and their target genes (TIR1, AFB1, AFB2, and AFB3) was transcriptionally regulated by H2S, and was related with H2S-induced antibacterial resistance. Moreover, H2S regulated 50 carbon metabolites including amino acids, organic acids, sugars, sugar alcohols, and aromatic amines. Taken together, these results indicated that cysteine desulfhydrase and H2S conferred abiotic stress tolerance and biotic stress resistance, via affecting the stress-related gene expressions, ROS metabolism, metabolic homeostasis, and MIR393-targeted auxin receptors. PMID:25329496

  19. MICROSCALE METABOLIC, REDOX AND ABIOTIC REACTIONS IN HANFORD 300 AREA SUBSURFACE SEDIMENTS

    Energy Technology Data Exchange (ETDEWEB)

    Beyenal, Haluk [WSU; McLEan, Jeff [JCVI; Majors, Paul [PNNL; Fredrickson, Jim [PNNL

    2013-11-14

    The Hanford 300 Area is a unique site due to periodic hydrologic influence of river water resulting in changes in groundwater elevation and flow direction. This area is also highly subject to uranium remobilization, the source of which is currently believed to be the region at the base of the vadose zone that is subject to period saturation due to the changes in the water levels in the Columbia River. We found that microbial processes and redox and abiotic reactions which operate at the microscale were critical to understanding factors controlling the macroscopic fate and transport of contaminants in the subsurface. The combined laboratory and field research showed how microscale conditions control uranium mobility and how biotic, abiotic and redox reactions relate to each other. Our findings extended the current knowledge to examine U(VI) reduction and immobilization using natural 300 Area communities as well as selected model organisms on redox-sensitive and redox-insensitive minerals. Using innovative techniques developed specifically to probe biogeochemical processes at the microscale, our research expanded our current understanding of the roles played by mineral surfaces, bacterial competition, and local biotic, abiotic and redox reaction rates on the reduction and immobilization of uranium.

  20. Elements as Direct Feedstocks for Organic Synthesis: Fe/I2/O2 for Diamination of 2-Cyclohexenones with 2-Aminopyrimidine and 2-Aminopyridines.

    Science.gov (United States)

    Nguyen, Thanh Binh; Corbin, Mathilde; Retailleau, Pascal; Ermolenko, Ludmila; Al-Mourabit, Ali

    2015-10-16

    Elements as feedstocks for organic synthesis, the trio of metallic iron, molecular iodine, and dioxygen, were found to be an excellent tool for oxidative regioselective diamination of conjugated enones with 2-aminopyrimidine (a guanidine surrogate) and 2-aminopyridines leading to unaromatized coupled products in moderate to good yields. PMID:26418069