Sample records for abiotic organic synthesis

  1. Deep Carbon Cycling in the Deep Hydrosphere: Abiotic Organic Synthesis and Biogeochemical Cycling (United States)

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


    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.

  2. 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


    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.

  3. Experimental Study of Abiotic Organic Synthesis at High Temperature and Pressure Conditions: Carbon Isotope and Mineral Surface Characterizations (United States)

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


    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

  4. Abiotic Bromination of Soil Organic Matter

    Energy Technology Data Exchange (ETDEWEB)

    Leri, Alessandra C.; Ravel, Bruce


    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.

  5. Experimental Evidence for Abiotic Sulfurization of Marine Dissolved Organic Matter

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    Anika M. Pohlabeln


    Full Text Available Dissolved organic sulfur (DOS is the largest pool of organic sulfur in the oceans, and as such it is an important component of the global sulfur cycle. DOS in the ocean is resistant against microbial degradation and turns over on a millennium time scale. However, sources and mechanisms behind its stability are largely unknown. Here, we hypothesize that in sulfate-reducing sediments sulfur is abiotically incorporated into dissolved organic matter (DOM and released to the ocean. We exposed natural seawater and the filtrate of a plankton culture to sulfidic conditions. Already after 1-h at 20°C, DOS concentrations had increased 4-fold in these experiments, and 14-fold after 4 weeks at 50°C, indicating that organic matter does not need long residence times in natural sulfidic environments to be affected by sulfurization. Molecular analysis via ultrahigh-resolution mass spectrometry showed that sulfur was covalently and unselectively bound to DOM. Experimentally produced and natural DOS from sediments were highly similar on a molecular and structural level. By combining our data with published benthic DOC fluxes we estimate that 30–200 Tg DOS are annually transported from anaerobic and sulfate reducing sediments to the oceans. Uncertainties in this first speculative assessment are large. However, this first attempt illustrates that benthic DOS flux is potentially one order of magnitude larger than that via rivers indicating that this could balance the estimated global net removal of refractory DOS.

  6. Abiotic enantiomerization of permethrin and cypermethrin: effects of organic solvents. (United States)

    Qin, Sujie; Gan, Jianying


    All synthetic pyrethroids are chiral compounds, and isomerization has been frequently observed from exposure to certain solvents. However, so far, pyrethroid isomerization caused by solvents has not been characterized at the enantiomer level. In this study, we evaluated the occurrence of enantiomerization of two commonly used pyrethroids, permethrin and cypermethrin, in various organic solvents and solvent-water systems. The four stereoisomers of permethrin were stable under all test conditions. Rapid enantiomerization of cypermethrin was observed in isopropanol and methanol but not in n-hexane, acetone, or methylene chloride. After 4 days at room temperature, 18-39% conversions occurred for the different cypermethrin stereoisomers in isopropanol and methanol, and the enantiomerization invariably took place at the alpha-carbon position. The extent of enantiomerization was affected by temperature dependence and was also influenced by water as a cosolvent. In solvent-water mixtures, cypermethrin underwent gradual enantiomerization in acetone-water and rapid enantiomerization in isopropanol-water or methanol-water. The extent of enantiomerization varied among the solvents and as a function of the solvent-to-water ratio. Results from this study suggest that exposure to certain solvents and water may cause artifacts in chiral analysis and that for isomer-enriched pyrethroid products, such abiotic enantiomerization may render the products less effective because the conversion leads to the formation of inactive stereoisomers.

  7. 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.


    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

  8. Abiotic Synthesis of Nucleic Acids: Hypochromicity and Future Research (United States)

    Glass, K.; Oye, M.; Deamer, D.; Vercoutere, W.


    The earliest forms of life would likely have a protocellular form, with a membrane encapsulating some form of linear charged polymer. These polymers could have enzymatic as well as genetic properties. We can simulate plausible prebiotic conditions in the laboratory to test hypotheses related to this concept. In earlier work we have shown that mononucleotides organized within a multilamellar lipid matrix can produce oligomers in the anhydrous phase of dehydration- rehydration cycles (Rajamani, 2008). If mononucleotides are in solution at millimolar concentrations, then oligomers resembling RNA are synthesized and exist in a steady state with their monomers DeGuzman, 2014). We have used conventional and novel techniques to demonstrate that secondary structures stabilized by hydrogen bonds may be present in the condensation products produced in dehydration- rehydration cycles that simulate hydrothermal fields that were present on the early Earth. Gel electrophoresis data corroborates the presence of up to 200-base pair length RNA fragments in products of Hydration-Dehydration experiments. Furthermore, hypochromicity measurements demonstrate a degree of hypochromicity found in single RNA strand of known sequence, as well as results that indicate this is true also for a sample of complementary strands of RNA. Analysis of ionic current signatures of known RNA hairpin molecule as measured using a nanopore detector indicate a significant variability in pattern, different from the signatures produced by DNA hairpin molecules. This informs how we may interpret nanopore data gathered from prebiotic simulations.

  9. Sterility Caused by Floral Organ Degeneration and Abiotic Stresses in Arabidopsis and Cereal Grains

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    Ashley Rae Smith


    Full Text Available Natural floral organ degeneration or abortion results in unisexual or fully sterile flowers, while abiotic stresses lead to sterility after initiation of floral reproductive organs. Since normal flower development is essential for plant sexual reproduction and crop yield, it is imperative to have a better understanding of plant sterility under regular and stress conditions. Here, we review the functions of ABC genes together with their downstream genes in floral organ degeneration and the formation of unisexual flowers in Arabidopsis and several agriculturally significant cereal grains. We further explore the roles of hormones, including auxin, brassinosteroids, jasmonic acid, gibberellic acid, and ethylene, in floral organ formation and fertility. We show that alterations in genes affecting hormone biosynthesis, hormone transport and perception cause loss of stamens/carpels, abnormal floral organ development, poor pollen production, which consequently result in unisexual flowers and male/female sterility. Moreover, abiotic stresses, such as heat, cold, and drought, commonly affect floral organ development and fertility. Sterility is induced by abiotic stresses mostly in male floral organ development, particularly during meiosis, tapetum development, anthesis, dehiscence, and fertilization. A variety of genes including those involved in heat shock, hormone signaling, cold tolerance, metabolisms of starch and sucrose, meiosis, and tapetum development are essential for plants to maintain normal fertility under abiotic stress conditions. Further elucidation of cellular, biochemical and molecular mechanisms about regulation of fertility will improve yield and quality for many agriculturally valuable crops.

  10. Abiotic origin of biopolymers (United States)

    Oro, J.; Stephen-Sherwood, E.


    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.

  11. Organic Synthesis using Clay Catalysts

    Indian Academy of Sciences (India)

    His work includes organic synthesis and reaction mechanisms mainly in the area of organosilicon chemistry. Presently he is also working on organic synthesis under solvent- free conditions and using clay-catalyses. Keywords. Montmorillonite, ion-exchange, clay-nanomaterials, dehydration pyrolysis, rearrangement, steric.

  12. Ureidopyrazine Derivatives: Synthesis and Biological Evaluation as Anti-Infectives and Abiotic Elicitors

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    Ghada Bouz


    Full Text Available Tuberculosis (TB caused by Mycobacterium tuberculosis (Mtb has become a frequently deadly infection due to increasing antimicrobial resistance. This serious issue has driven efforts worldwide to discover new drugs effective against Mtb. One research area is the synthesis and evaluation of pyrazinamide derivatives as potential anti-TB drugs. In this paper we report the synthesis and biological evaluations of a series of ureidopyrazines. Compounds were synthesized by reacting alkyl/aryl isocyanates with aminopyrazine or with propyl 5-aminopyrazine-2-carboxylate. Reactions were performed in pressurized vials using a CEM Discover microwave reactor with a focused field. Purity and chemical structures of products were assessed, and the final compounds were tested in vitro for their antimycobacterial, antibacterial, and antifungal activities. Propyl 5-(3-phenylureidopyrazine-2-carboxylate (compound 4, MICMtb = 1.56 μg/mL, 5.19 μM and propyl 5-(3-(4-methoxyphenylureidopyrazine-2-carboxylate (compound 6, MICMtb = 6.25 μg/mL, 18.91 μM had high antimycobacterial activity against Mtb H37Rv with no in vitro cytotoxicity on HepG2 cell line. Therefore 4 and 6 are suitable for further structural modifications that might improve their biological activity and physicochemical properties. Based on the structural similarity to 1-(2-chloropyridin-4-yl-3-phenylurea, a known plant growth regulator, two selected compounds were evaluated for similar activity as abiotic elicitors.

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

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    Gábor Kocsy


    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.

  14. Acidity and organic matter stimulate abiotic nitric oxide emissions in drying soils (United States)

    Homyak, P. M.; Kamiyama, M. T.; Sickman, J. O.; Schimel, J.


    Soils are an important source of nitric oxide (NO) to the atmosphere, particularly in dry lands because of tradeoffs that develop between biotic and abiotic NO-producing processes as soils dry. Understanding how increasingly drier climates may offset the balance of these tradeoffs is critical to estimating N budgets, especially because regions on Earth are expected to become drier. We measured NO emission pulses after wetting soils from similar lithologies along an altitudinal gradient in the Sierra Nevada, CA, where mean annual precipitation varied from 670 to 1,500 mm. Along the gradient, we measured field NO emissions, and used chloroform in the laboratory to partition between biotic and abiotic NO-producing processes. Field NO emission pulses were lowest in acidic and organic matter-rich soils (4-72 ng NO-N m-2 s-1), presumably because topography and vegetation influenced soil moisture and substrate availability, but were highest in the high-elevation barren site ( 560 ng NO-N m-2 s-1). In the laboratory, NO emission pulses were up to 19× greater in chloroform-treated soils than in the controls, and in contrast to field measurements, these pulses increased with elevation as pH decreased (6.2 to 4.4) and soil organic matter (SOM) increased (18 to 157 mg C g-1). Drought can favor abiotic NO-producing processes (i.e., chemodenitrification) during periods when biological processes become stressed. Acidic and SOM-rich soils, which typically develop under mesic conditions, are most vulnerable to N loss as interactions between drought, acidity, and SOM stimulate chemodenitrification.

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

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    H. L. Throop


    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.

  16. Abiotic synthesis of RNA in water: a common goal of prebiotic chemistry and bottom-up synthetic biology. (United States)

    Cafferty, Brian J; Hud, Nicholas V


    For more than half a century chemists have searched for a plausible prebiotic synthesis of RNA. The initial advances of the 1960s and 1970s were followed by decades of measured progress and a growing pessimism about overcoming remaining challenges. Fortunately, the past few years have provided a number of important advances, including new abiotic routes for the synthesis of nucleobases, nucleosides, and nucleotides. Recent discoveries also provide additional support for the hypothesis that RNA is the product of evolution, being preceded by ancestral genetic polymers, or pre-RNAs, that are synthesized more easily than RNA. In some cases, parallel searches for plausible prebiotic routes to RNA and pre-RNAs have provided more than one experimentally verified synthesis of RNA substructures and possible predecessors. Just as the synthesis of a contemporary biological molecule cannot be understood without knowledge of cellular metabolism, it is likely that an integrated approach that takes into account both plausible prebiotic reactions and plausible prebiotic environments will ultimately provide the most satisfactory and unifying chemical scenarios for the origin of nucleic acids. In this context, recent advances towards the abiotic synthesis of RNA and candidates for pre-RNAs are beginning to suggest that some molecules (e.g., urea) were multi-faceted contributors to the origin of nucleic acids, and the origin of life. Copyright © 2014 Elsevier Ltd. All rights reserved.

  17. Analysis of Cell Wall-Related Genes in Organs of Medicago sativa L. under Different Abiotic Stresses. (United States)

    Behr, Marc; Legay, Sylvain; Hausman, Jean-Francois; Guerriero, Gea


    Abiotic constraints are a source of concern in agriculture, because they can have a strong impact on plant growth and development, thereby affecting crop yield. The response of plants to abiotic constraints varies depending on the type of stress, on the species and on the organs. Although many studies have addressed different aspects of the plant response to abiotic stresses, only a handful has focused on the role of the cell wall. A targeted approach has been used here to study the expression of cell wall-related genes in different organs of alfalfa plants subjected for four days to three different abiotic stress treatments, namely salt, cold and heat stress. Genes involved in different steps of cell wall formation (cellulose biosynthesis, monolignol biosynthesis and polymerization) have been analyzed in different organs of Medicago sativa L. Prior to this analysis, an in silico classification of dirigent/dirigent-like proteins and class III peroxidases has been performed in Medicago truncatula and M. sativa. The final goal of this study is to infer and compare the expression patterns of cell wall-related genes in response to different abiotic stressors in the organs of an important legume crop.

  18. Organic Synthesis using Clay Catalysts

    Indian Academy of Sciences (India)

    Home; Journals; Resonance – Journal of Science Education; Volume 7; Issue 1. Organic Synthesis using Clay Catalysts - Clays for 'Green Chemistry'. Gopalpur Nagendrappa. General Article Volume 7 Issue 1 January 2002 pp 64-77. Fulltext. Click here to view fulltext PDF. Permanent link:

  19. Surprising results from abiotic enzyme digestion of dissolved organic matter at the molecular scale (United States)

    Hess, N. J.; Tfaily, M. M.; Heredia-Langnar, A.; Rodriguez, L.; Purvine, E.; Todd-Brown, K. E.


    Sometimes even the simplest of experiments leads to unexpected results and new understanding. We extract dissolved organic matter using water from peat soil obtained from the S1 bog at the Marcell Experimental Forest in northern Minnesota. We characterized the dissolved organic matter in the water extract before and after adding glucosidase, peroxidase and β-N-Acetylglucosaminidase enzymes using electrospray Fourier transform ion cyclotron resonance mass spectrometry in negative ion mode. Based on mass measurement accuracy of less than 1 ppm for singly charged ions, we assigned putative chemical formula to greater than 80% of the measured mass spectrometry features. For each enzyme tested we are able to easily distinguish between the types and composition of dissolved organic molecules that are susceptible to enzyme degradation - and those that are not - based on the presence new compounds in reacted extracts and loss of compounds from the initial water extract. Next, we created a consensus molecular network analysis based on the neutral mass loss between the measured compounds for each enzyme. The connectivity within these networks suggested a unique, distinctive chemistry for each enzyme. Some results were expected, like the nondiscriminatory oxidation of organic molecules by peroxidase and preferential loss of lignin and tannin-like molecules by glucosidase. However, surprising results include the apparent reactivity of glucosidase enzymatic products to reassemble, forming larger mass organic molecules. While these experiments were conducted abiotically, these molecular-resolved results suggest that biotic enzymatic processes may result in product compounds with unexpected chemistry and reactivity, implying that our current conceptual model of microbial enzymatic activity may be overly simplistic.

  20. Molecular mechanisms in plant abiotic stress response

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    Poltronieri Palmiro


    Full Text Available Improved crop varieties are needed to sustain the food supply, to fight climate changes, water scarcity, temperature increase and a high variability of rainfalls. Variability of drought and increase in soil salinity have negative effects on plant growth and abiotic stresses seriously threaten sustainable agricultural production. To overcome the influence of abiotic stresses, new tolerant plant varieties and breeding techniques using assisted selection are sought. A deep understanding of the mechanisms that respond to stress and sustain stress resistance is required. Here is presented an overview of several mechanisms that interact in the stress response. Localised synthesis of plant hormones, second messengers and local effectors of abiotic stress response and survival, the signaling pathways regulated by plant hormones are today better understood. Metabolic networks in drought stress responses, long distance signaling, cross-talk between plant organs finalised to tissue-specific expression of abiotic stress relieving genes have been at the centre of most recent studies.

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

  2. Machine-Assisted Organic Synthesis. (United States)

    Ley, Steven V; Fitzpatrick, Daniel E; Myers, Rebecca M; Battilocchio, Claudio; Ingham, Richard J


    In this Review we describe how the advent of machines is impacting on organic synthesis programs, with particular emphasis on the practical issues associated with the design of chemical reactors. In the rapidly changing, multivariant environment of the research laboratory, equipment needs to be modular to accommodate high and low temperatures and pressures, enzymes, multiphase systems, slurries, gases, and organometallic compounds. Additional technologies have been developed to facilitate more specialized reaction techniques such as electrochemical and photochemical methods. All of these areas create both opportunities and challenges during adoption as enabling technologies. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. ABA and GA3 regulate the synthesis of primary and secondary metabolites related to alleviation from biotic and abiotic stresses in grapevine. (United States)

    Murcia, Germán; Fontana, Ariel; Pontin, Mariela; Baraldi, Rita; Bertazza, Gianpaolo; Piccoli, Patricia N


    Plants are able to synthesize a large number of organic compounds. Among them, primary metabolites are known to participate in plant growth and development, whereas secondary metabolites are mostly involved in defense and other facultative processes. In grapevine, one of the major fruit crops in the world, secondary metabolites, mainly polyphenols, are of great interest for the wine industry. Even though there is an extensive literature on the content and profile of those compounds in berries, scarce or no information is available regarding polyphenols in other organs. In addition, little is known about the effect of plant growth regulators (PGRs), ABA and GA3 (extensively used in table grapes) on the synthesis of primary and secondary metabolites in wine grapes. In table grapes, cultural practices include the use of GA3 sprays shortly before veraison, to increase berry and bunch size, and sugar content in fruits. Meanwhile, ABA applications to the berries on pre-veraison improve the skin coloring and sugar accumulation, anticipating the onset of veraison. Accordingly, the aim of this study was to assess and characterize primary and secondary metabolites in leaves, berries and roots of grapevine plants cv. Malbec at veraison, and changes in compositions after ABA and GA3 aerial sprayings. Metabolic profiling was conducted using GC-MS, GC-FID and HPLC-MWD. A large set of metabolites was identified: sugars, alditols, organic acids, amino acids, polyphenols (flavonoids and non-flavonoids) and terpenes (mono-, sesqui-, di- and triterpenes). The obtained results showed that ABA applications elicited synthesis of mono- and sesquiterpenes in all assessed tissues, as well as L-proline, acidic amino acids and anthocyanins in leaves. Additionally, applications with GA3 elicited synthesis of L-proline in berries, and mono- and sesquiterpenes in all the tissues. However, treatment with GA3 seemed to block polyphenol synthesis, mainly in berries. In conclusion, ABA and GA3

  4. Abiotic synthesis of purines and other heterocyclic compounds by the action of electrical discharges (United States)

    Yuasa, S.; Flory, D.; Basile, B.; Oro, J.


    The synthesis of purines and pyrimidines using Oparin-Urey-type primitive earth atmospheres has been demonstrated by reacting methane, ethane, and ammonia in electrical discharges. Adenine, guaine, 4-aminoimidazole-5-carboxamide (AICA), and isocytosine have been identified by UV spectrometry and paper chromatography as the products of the reaction. The total yields of the identified heterocyclic compounds are 0.0023 percent. It is concluded that adenine synthesis occurs at a much lower concentration of hydrogen cyanide than has been shown by earlier studies. Pathways for the synthesis of purines from hydrogen cyanide are discussed, and a comparison of the heterocyclic compounds that have been identified in meteorites and in prebiotic reactions is presented.

  5. Fluid Mechanics Optimising Organic Synthesis (United States)

    Leivadarou, Evgenia; Dalziel, Stuart


    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.

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

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    Katarína Kráľová


    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.

  7. Surface chemistry allows for abiotic precipitation of dolomite at low temperature


    Roberts, Jennifer A.; Kenward, Paul A.; Fowle, David A.; Goldstein, Robert H.; González, Luis A.; Moore, David S.


    Abundant in the geologic record, but scarce in modern environments below 50 °C, the mineral dolomite is used to interpret ancient fluid chemistry, paleotemperature, and is a major hydrocarbon reservoir rock. Because laboratory synthesis of abiotic dolomite had been unsuccessful, chemical mechanisms for precipitation are poorly constrained, and limit interpretations of its occurrence. Here we report the abiotic synthesis of dolomite at 25 °C, and demonstrate that carboxylated surfaces on organ...

  8. The abiotic degradation of methyl parathion in anoxic sulfur-containing system mediated by natural organic matter. (United States)

    Liao, Xiaoping; Zhang, Caixiang; Wang, Yanxin; Tang, Mi


    Although the kinetics and transformation of methyl parathion have been investigated extensively, its abiotic degradation mechanism in anoxic sulfur-containing groundwater system is still not clear. In this work, the abiotic degradation of methyl parathion in anoxic sulfur-containing system mediated by natural organic matter (NOM) was investigated in batch experiments. It was found that the removal of methyl parathion (up to 80.7%) was greatly improved in sulfide containing NOM compared to those in sulfide alone (with 15.5%) and in NOM alone (almost negligible). Various sulfur species presented significant differences in behaviors methyl parathion degradation, but followed by the pseudo-first-order model well. No facilitated degradation of methyl parathion was observed in sulfite (SO32-) or thiosulfate (S2O32-) containing NOM such as anthraquinone. Although elemental sulfur (S0) and cysteine could further improve the degradation rate of methyl parahtion, their impacts was very limited. The removal efficiency of methyl parathion in anoxic sulfur-containing system were related remarkably with NOM concentration and solution pH. Based on the transformation products identified by gas chromatography-mass spectrometer (GC/MS) and liquid chromatography high resolution mass spectrometer (LC/HRMS), both the nitro group reduction and hydrolysis (SN@C) processes by sulfide (HS-) were further proved to be two predominant reaction mechanisms for the abiotic degradation of methyl parathion in anoxic sulfur-containing system. The results of this study help to understand the natural attenuation of methyl parathion under anoxic sulfide-containing groundwater system mediated by NOM. Copyright © 2017 Elsevier Ltd. All rights reserved.

  9. Comparison of bacterial cells and amine-functionalized abiotic surfaces as support for Pd nanoparticle synthesis

    DEFF Research Database (Denmark)

    De Corte, Simon; Bechstein, Stefanie; Lokanathan, Arcot R.


    An increasing demand for catalytic Pd nanoparticles has motivated the search for sustainable production methods. An innovative approach uses bacterial cells as support material for synthesizing Pd nanoparticles by reduction of Pd(II) with e.g. hydrogen or formate. Nevertheless, drawbacks of micro......An increasing demand for catalytic Pd nanoparticles has motivated the search for sustainable production methods. An innovative approach uses bacterial cells as support material for synthesizing Pd nanoparticles by reduction of Pd(II) with e.g. hydrogen or formate. Nevertheless, drawbacks...... of microbially supported Pd catalysts are the low catalytic activity compared to conventional Pd nanocatalysts and the possible poisoning of the catalyst surface by sulfur originating from bacterial proteins. A recent study showed that amine groups were a key component in surface-supported synthesis of Pd...... materials were visualized by transmission electron microscopy, and their activity was evaluated by catalysis of p-nitrophenol reduction. Surfaces functionalized with 3-aminopropyltriethoxysilane and chitosan were interesting alternatives to bacterial cells, as the catalytic activity of Pd particles formed...

  10. Synthesis Road Map Problems in Organic Chemistry (United States)

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


    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…

  11. 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


    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

  12. Defining reference genes in Oryza sativa using organ, development, biotic and abiotic transcriptome datasets

    Directory of Open Access Journals (Sweden)

    Whelan James


    Full Text Available Abstract Background Reference genes are widely used to normalise transcript abundance data determined by quantitative RT-PCR and microarrays. However, the approaches taken to define reference genes can be variable. Although Oryza sativa (rice is a widely used model plant and important crop specie, there has been no comprehensive analysis carried out to define superior reference genes. Results Analysis of 136 Affymetrix transcriptome datasets comprising of 373 genome microarrays from studies in rice that encompass tissue, developmental, abiotic, biotic and hormonal transcriptome datasets identified 151 genes whose expression was considered relatively stable under all conditions. A sub-set of 12 of these genes were validated by quantitative RT-PCR and were seen to be stable under a number of conditions. All except one gene that has been previously proposed as a stably expressed gene for rice, were observed to change significantly under some treatment. Conclusion A new set of reference genes that are stable across tissue, development, stress and hormonal treatments have been identified in rice. This provides a superior set of reference genes for future studies in rice. It confirms the approach of mining large scale datasets as a robust method to define reference genes, but cautions against using gene orthology or counterparts of reference genes in other plant species as a means of defining reference genes.

  13. Tuning the Protein Corona of Hydrogel Nanoparticles: The Synthesis of Abiotic Protein and Peptide Affinity Reagents. (United States)

    O'Brien, Jeffrey; Shea, Kenneth J


    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

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

    Energy Technology Data Exchange (ETDEWEB)

    He, Wei [Department of Environment and Energy, Sejong University, Seoul 143-747 (Korea, Republic of); Choi, Ilhwan [Water Analysis and Research Center, K-water, 560 Sintanjin-ro, Daedeok-gu, Daejeon 307-711 (Korea, Republic of); Lee, Jung-Joon [Department of Biological Education, Daegu University, Gyungbuk 712-714 (Korea, Republic of); Hur, Jin, E-mail: [Department of Environment and Energy, Sejong University, Seoul 143-747 (Korea, Republic of)


    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-C L{sup −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. - Highlights: • Humic fractions varied

  15. Abiotic vs biological sources and fates of organic compounds in a low temperature continental serpentinizing system (United States)

    Robinson, K.; Noble, S. M.; Shock, E.


    Serpentinization is likely the most common water-rock reaction in our solar system. During this process ultramafic silicates are hydrated, a calcium hydroxide solution is formed, and H2O is reduced to H2 coupled to the oxidation of Fe2+ to Fe3+. The resulting hyper-alkaline, reduced conditions generate thermodynamic drives for numerous carbon compound reactions, including the precipitation of various carbonate minerals and the reduction of inorganic carbonate to organic carbon. Testing the extent to which these thermodynamic drives lead to observable results led to the present study of the flow and transformations of carbon through the active continental serpentinizing system at the Samail Ophiolite in the Sultanate of Oman. Water samples were collected from shallow groundwater (representing system input), hyper-alkaline seeps (system output), boreholes (system intermediate), and surface fluid mixing zones, and analyzed for concentrations of dissolved inorganic carbon (DIC + δ13C), organic carbon (+ δ13C), formate, acetate, H2, methane (+ δ13C), ethane, and an accompanying suite of other geochemical solutes. These analyses indicate that the vast majority of DIC in these serpentinizing fluids precipitates in the subsurface as carbonate minerals; however, a significant amount of DIC is converted into organic acids and light hydrocarbons and expelled at the surface in hyper-alkaline seeps. Based on thermodynamic calculations, it seems most likely that formate last equilibrated with dolomite (CaMg[CO3]2) in the subsurface, acetate last equilibrated with calcite (CaCO3) near the surface, and methane and ethane last equilibrated in a distinct carbon-limited region of the subsurface. As for the fates of these compounds, energetic calculations reveal that a combination of oxidative, reductive, and fermentative metabolisms are thermodynamically favorable. Indeed, δ13C trends record microbial methane oxidation at the surface and cannot rule out methane as biologically

  16. Pyrolysis-GCMS Analysis of Solid Organic Products from Catalytic Fischer-Tropsch Synthesis Experiments (United States)

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


    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.

  17. 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.


    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.

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

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


    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 (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.

  19. Carbon Isotope Systematics in Mineral-Catalyzed Hydrothermal Organic Synthesis Processes at High Temperature and Pressures (United States)

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


    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.

  20. Silver Cluster Catalysts for Green Organic Synthesis


    Shimizu, Ken-ichi; Satsuma, Atsushi


    Development of platinum-group-metal (PGM)-free  catalysts for green chemical synthesis is an important topic in synthetic catalysis, because PGM will soon be in short supply in the near future. Our group has paid attention to the catalytic functions of Ag clusters. Here, we summarize our recent work on size- and support-specific catalysis of Ag clusters for green organic synthesis. Ag clusters supported on Al2O3 act as effective heterogeneous catalysts for (1) oxidant-free dehydrogenation of ...

  1. Alkoxyallenes as building blocks for organic synthesis. (United States)

    Zimmer, Reinhold; Reissig, Hans-Ulrich


    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.

  2. Homeologous genes involved in mannitol synthesis reveal unequal contributions in response to abiotic stress in Coffea arabica. (United States)

    de Carvalho, Kenia; Petkowicz, Carmen L O; Nagashima, Getulio T; Bespalhok Filho, João C; Vieira, Luiz G E; Pereira, Luiz F P; Domingues, Douglas S


    Polyploid plants can exhibit transcriptional modulation in homeologous genes in response to abiotic stresses. Coffea arabica, an allotetraploid, accounts for 75% of the world's coffee production. Extreme temperatures, salinity and drought limit crop productivity, which includes coffee plants. Mannitol is known to be involved in abiotic stress tolerance in higher plants. This study aimed to investigate the transcriptional responses of genes involved in mannitol biosynthesis and catabolism in C. arabica leaves under water deficit, salt stress and high temperature. Mannitol concentration was significantly increased in leaves of plants under drought and salinity, but reduced by heat stress. Fructose content followed the level of mannitol only in heat-stressed plants, suggesting the partitioning of the former into other metabolites during drought and salt stress conditions. Transcripts of the key enzymes involved in mannitol biosynthesis, CaM6PR, CaPMI and CaMTD, were modulated in distinct ways depending on the abiotic stress. Our data suggest that changes in mannitol accumulation during drought and salt stress in leaves of C. arabica are due, at least in part, to the increased expression of the key genes involved in mannitol biosynthesis. In addition, the homeologs of the Coffea canephora subgenome did not present the same pattern of overall transcriptional response, indicating differential regulation of these genes by the same stimulus. In this way, this study adds new information on the differential expression of C. arabica homeologous genes under adverse environmental conditions showing that abiotic stresses can influence the homeologous gene regulation pattern, in this case, mainly on those involved in mannitol pathway.

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

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


    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. Exposure of gnotobiotic Artemia franciscana larvae to abiotic stress promotes heat shock protein 70 synthesis and enhances resistance to pathogenic Vibrio campbellii (United States)

    Pineda, Carlos; MacRae, Thomas H.; Sorgeloos, Patrick; Bossier, Peter


    Larvae of the brine shrimp Artemia franciscana serve as important feed in fish and shellfish larviculture; however, they are subject to bacterial diseases that devastate entire populations and consequently hinder their use in aquaculture. Exposure to abiotic stress was shown previously to shield Artemia larvae against infection by pathogenic Vibrio, with the results suggesting a mechanistic role for heat shock protein 70. In the current report, combined hypothermic/hyperthermic shock followed by recovery at ambient temperature induced Hsp70 synthesis in Artemia larvae. Thermotolerance was also increased as was protection against infection by Vibrio campbellii, the latter indicated by reduced mortality and lower bacterial load in challenge tests. Resistance to Vibrio improved in the face of declining body mass as demonstrated by measurement of ash-free dry weight. Hypothermic stress only and acute osmotic insult did not promote Hsp70 expression and thermotolerance in Artemia larvae nor was resistance to Vibrio challenge augmented. The data support a causal link between Hsp70 accumulation induced by abiotic stress and enhanced resistance to infection by V. campbellii, perhaps via stimulation of the Artemia immune system. This possibility is now under investigation, and the work may reveal fundamental properties of crustacean immunity. Additionally, the findings are important in aquaculture where development of procedures to prevent bacterial infection of feed stock such as Artemia larvae is a priority. PMID:18347942

  5. Organic synthesis in experimental impact shocks (United States)

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


    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.

  6. Synthesis-Spectroscopy Roadmap Problems: Discovering Organic Chemistry (United States)

    Kurth, Laurie L.; Kurth, Mark J.


    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…

  7. Novel Aryne Chemistry in Organic Synthesis

    Energy Technology Data Exchange (ETDEWEB)

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


    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

  8. Organic synthesis: march of the machines. (United States)

    Ley, Steven V; Fitzpatrick, Daniel E; Ingham, Richard J; Myers, Rebecca M


    Organic synthesis is changing; in a world where budgets are constrained and the environmental impacts of practice are scrutinized, it is increasingly recognized that the efficient use of human resource is just as important as material use. New technologies and machines have found use as methods for transforming the way we work, addressing these issues encountered in research laboratories by enabling chemists to adopt a more holistic systems approach in their work. Modern developments in this area promote a multi-disciplinary approach and work is more efficient as a result. This Review focuses on the concepts, procedures and methods that have far-reaching implications in the chemistry world. Technologies have been grouped as topics of opportunity and their recent applications in innovative research laboratories are described. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Flow “Fine” Synthesis: High Yielding and Selective Organic Synthesis by Flow Methods (United States)


    Abstract The concept of flow “fine” synthesis, that is, high yielding and selective organic synthesis by flow methods, is described. Some examples of flow “fine” synthesis of natural products and APIs are discussed. Flow methods have several advantages over batch methods in terms of environmental compatibility, efficiency, and safety. However, synthesis by flow methods is more difficult than synthesis by batch methods. Indeed, it has been considered that synthesis by flow methods can be applicable for the production of simple gasses but that it is difficult to apply to the synthesis of complex molecules such as natural products and APIs. Therefore, organic synthesis of such complex molecules has been conducted by batch methods. On the other hand, syntheses and reactions that attain high yields and high selectivities by flow methods are increasingly reported. Flow methods are leading candidates for the next generation of manufacturing methods that can mitigate environmental concerns toward sustainable society. PMID:26337828

  10. Organic or organometallic template mediated clay synthesis

    Energy Technology Data Exchange (ETDEWEB)

    Gregar, K.C.; Winans, R.E.; Botto, R.E.


    A method is given for incorporating diverse varieties of intercalants or templates directly during hydrothermal synthesis of clays such as hectorite or montmorillonite-type layer-silicate clays. For a hectorite layer-silicate clay, refluxing a gel of silica sol, magnesium hydroxide sol and LiF for 2 days with an organic or organometallic intercalant or template results in crystalline products containing either (a) organic dye molecules such as ethyl violet and methyl green, (b) dye molecules such as alcian blue based on a Cu(II)-phthalocyannine complex, or (c) transition metal complexes such as Ru(II)phenanthroline and Co(III)sepulchrate or (d) water-soluble porphyrins and metalloporphyrins. Montmorillonite-type clays are made by the method taught by US patent No. 3,887,454 issued to Hickson, June 13, 1975; however, a variety of intercalants or templates may be introduced. The intercalants or templates should have water-solubility, positive charge, and thermal stability under moderately basic (pH 9-10) aqueous reflux conditions or hydrothermal pressurized conditions for the montmorillonite-type clays.

  11. Stepwise Synthesis of Metal-Organic Frameworks. (United States)

    Bosch, Mathieu; Yuan, Shuai; Rutledge, William; Zhou, Hong-Cai


    Metal-organic frameworks (MOFs) are a category of porous materials that offer unparalleled control over their surface areas (demonstrated as higher than for any other material), pore characteristics, and functionalization. This allows them to be customized for exceptional performance in a wide variety of applications, most commonly including gas storage and separation, drug delivery, luminescence, or heterogeneous catalysis. In order to optimize biomimicry, controlled separations and storage of small molecules, and detailed testing of structure-property relationships, one major goal of MOF research is "rational design" or "pore engineering", or precise control of the placement of multiple functional groups in pores of chosen sizes and shapes. MOF crystal growth can be controlled through judicious design of stepwise synthetic routes, which can also allow functionalization of MOFs in ways that were previously synthetically inaccessible. Organic chemists have developed a library of powerful techniques over the last century, allowing the total synthesis and detailed customization of complex molecules. Our hypothesis is that total synthesis is also possible for customized porous materials, through the development of similar multistep techniques. This will enable the rational design of MOFs, which is a major goal of many researchers in the field. We have begun developing a library of stepwise synthetic techniques for MOFs, allowing the synthesis of ultrastable MOFs with multiple crystallographically ordered and customizable functional groups at controlled locations within the pores. In order to design MOFs with precise control over pore size and shape, stability, and the placement of multiple different functional groups within the pores at tunable distances from one another, we have concentrated on methods which allow us to circumvent the lack of control inherent to one-pot MOF crystallization. Kinetically tuned dimensional augmentation (KTDA) is an approach using

  12. Histidine as a catalyst in organic synthesis: A facile in situ synthesis ...

    Indian Academy of Sciences (India)

    Home; Journals; Journal of Chemical Sciences; Volume 113; Issue 4. Histidine as a catalyst in organic synthesis: A facile in situ synthesis of , N-diarylnitrones. H Mallesha K R Ravi Kumar B K Vishu Kumar K Mantelingu K S Rangappa. Organic Volume 113 Issue 4 August 2001 pp 291-296 ...

  13. Synthesis of polyaryl rigid-core carbosilane dendrimers for supported organic synthesis

    NARCIS (Netherlands)

    Wander, M.; Hausoul, P.J.C.; Sliedregt, L.A.J.M.; van Steen, B.J.; van Koten, G.; Klein Gebbink, R.J.M.


    Carbosilane dendrimers can be used as soluble supports for organic synthesis, since their structure allows separation of excess reagents from the supported products, eventually yielding products of high purity and in high yield, as in solid-phase organic synthesis (SPOS). In previous studies often

  14. Enhanced biotic and abiotic transformation of Cr(vi) by quinone-reducing bacteria/dissolved organic matter/Fe(iii) in anaerobic environment. (United States)

    Huang, Bin; Gu, Lipeng; He, Huan; Xu, Zhixiang; Pan, Xuejun


    This study investigated the simultaneous transformation of Cr(vi) via a closely coupled biotic and abiotic pathway in an anaerobic system of quinone-reducing bacteria/dissolved organic matters (DOM)/Fe(iii). Batch studies were conducted with quinone-reducing bacteria to assess the influences of sodium formate (NaFc), electron shuttling compounds (DOM) and the Fe(iii) on Cr(vi) reduction rates as these chemical species are likely to be present in the environment during in situ bioremediation. Results indicated that the concentration of sodium formate and anthraquinone-2-sodium sulfonate (AQS) had apparently an effect on Cr(vi) reduction. The fastest decrease in rate for incubation supplemented with 5 mM sodium formate and 0.8 mM AQS showed that Fe(iii)/DOM significantly promoted the reduction of Cr(vi). Presumably due to the presence of more easily utilizable sodium formate, DOM and Fe(iii) have indirect Cr(vi) reduction capability. The coexisting cycles of Fe(ii)/Fe(iii) and DOM(ox)/DOM(red) exhibited a higher redox function than the individual cycle, and their abiotic coupling action can significantly enhance Cr(vi) reduction by quinone-reducing bacteria.

  15. Fundamentals and applications of organic electrochemistry synthesis, materials, devices

    CERN Document Server

    Fuchigami, Toshio; Inagi, Shinsuke


    This textbook is an accessible overview of the broad field of organic electrochemistry, covering the fundamentals and applications of contemporary organic electrochemistry.  The book begins with an introduction to the fundamental aspects of electrode electron transfer and methods for the electrochemical measurement of organic molecules. It then goes on to discuss organic electrosynthesis of molecules and macromolecules, including detailed experimental information for the electrochemical synthesis of organic compounds and conducting polymers. Later chapters highlight new methodology for organic electrochemical synthesis, for example electrolysis in ionic liquids, the application to organic electronic devices such as solar cells and LEDs, and examples of commercialized organic electrode processes. Appendices present useful supplementary information including experimental examples of organic electrosynthesis, and tables of physical data (redox potentials of various organic solvents and organic compounds and phy...

  16. Patterns in Organometallic Chemistry with Application in Organic Synthesis. (United States)

    Schwartz, Jeffrey; Labinger, Jay A.


    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…

  17. 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

    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

  18. Greener and Sustainable Trends in Synthesis of Organics and Nanomaterials (United States)

    Trends in greener and sustainable process development during the past 25 years are abridged involving the use of alternate energy inputs (mechanochemistry, ultrasound- or microwave irradiation), photochemistry, and greener reaction media as applied to synthesis of organics and na...

  19. Recent developments on ultrasound assisted catalyst-free organic synthesis. (United States)

    Banerjee, Bubun


    Mother Nature needs to be protected from ever increasing chemical pollutions associated with synthetic organic processes. The fundamental challenge for today's methodologists is to make their protocols more environmentally benign and sustainable by avoiding the extensive use of hazardous reagents and solvents, harsh reaction conditions, and toxic metal catalysts. However, the people of the twenty-first century are well aware about the side effects of those hazardous substances used and generated by the chemical processes. As a result, the last decade has seen a tremendous outburst in modifying chemical processes to make them 'sustainable' for the betterment of our environment. Catalysts play a crucial role in organic synthesis and thus they find huge applications and uses. Scientists' continuously trying to modify the catalysts to reduce their toxicity level, but the most benign way is to design an organic reaction without catalyst(s), if possible. It is worthy to mention that the involvement of ultrasound in organic synthesis is sometimes fulfilling this goal. In many occasions the applications of ultrasound can avoid the use of catalysts in organic reactions. Such beneficial features as a whole have motivated the organic chemists to apply ultrasonic irradiation in more heights and as a results, in recent past, there were immense applications of ultrasound in organic reactions for the synthesis of diverse organic scaffolds under catalyst-free condition. The present review summarizes the latest developments on ultrasound assisted catalyst-free organic synthesis reported so far. Copyright © 2016 Elsevier B.V. All rights reserved.

  20. Camera-enabled techniques for organic synthesis (United States)

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


    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

  1. 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


    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.

  2. 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.


    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.

  3. The validity of the Gammarus:Asellus ratio as an index of organic pollution: abiotic and biotic influences. (United States)

    MacNeil, Calum; Dick, Jaimie T A; Bigsby, Ewan; Elwood, Robert W; Montgomery, W Ian; Gibbins, Chris N; Kelly, David W


    In freshwaters. Gammarus spp. are more sensitive to organic pollution than Asellus spp. and the relative abundance of the two taxa has been proposed as a pollution index. We tested the validity of this by examining the relationship between the Gammarus: Asellus (G : A) ratio and (1) a suite of physico-chemical variables. (2) established biotic (average score per taxon, ASPT) and richness (species richness (S) and Ephemeroptera, Plecoptera and Trichoptera families richness (EPT family richness)) indices generated from the macroinvertebrate community. In addition, we investigated a suspected biotic interaction, predation, between Gammarus and Asellus. Both univariate and multivariate analyses showed that the G: A ratio was sometimes responsive to changes in parameters linked to organic pollution, such as BOD5 and nitrate levels. However, the G : A ratio also appeared responsive to variables not directly linked to organic pollution, such as conductivity and distance from source. There were significant positive correlations among the G : A ratio and the ASPT, S and EPT, indicating that changes in the relative abundances of Gammarus and Asellus were reflected in changes in the pollution sensitivity and richness of the wider macroinvertebrate community. A laboratory experiment revealed significant predation of Asellus aquaticus juveniles by Gammarus duebeni celticus adults, but no reciprocal predation. We propose that the G: A ratio may be useful as a crude measure of organic pollution that could supplement more complex indices in a multimetric approach to pollution monitoring or be used for monitoring individual sites, where a simple technique is required for monitoring purposes over a period of time. Also, we urge recognition of the possible role of biotic interactions among taxa used in the generation of pollution indices.

  4. Transitioning organic synthesis from organic solvents to water. What's your E Factor? (United States)

    Lipshutz, Bruce H.; Ghorai, Subir


    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

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

    CERN Document Server

    Torres, Tomas


    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. Organic synthesis with olefin metathesis catalysts

    Energy Technology Data Exchange (ETDEWEB)

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


    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.

  7. A biocompatible alkene hydrogenation merges organic synthesis with microbial metabolism. (United States)

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


    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. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. The 2010 Chemistry Nobel Prize: Pd (0)-Catalyzed Organic Synthesis

    Indian Academy of Sciences (India)

    Home; Journals; Resonance – Journal of Science Education; Volume 16; Issue 2. The 2010 Chemistry Nobel Prize: Pd(O)-Catalyzed Organic Synthesis. Gopalpur Nagendrappa Y C Sunil Kumar. General Article Volume 16 Issue 2 February 2011 pp 152-164 ...

  9. organic template free synthesis of zsm11 from kaolinite clay

    African Journals Online (AJOL)


    hydrocarbon, etc. Accordingly, this work present successful synthesis of zeolite ZSM11 from kaolinite clay, seeded with. NaY type zeolite and aged for 3-11 days, in an organic template free condition. The used kaolinite clays were sourced from two different mines in Nigeria, namely; Kankara and Onibode. They were both ...

  10. Synthesis of Bisphenol Z: An Organic Chemistry Experiment (United States)

    Gregor, Richard W.


    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…

  11. Synthesis and Chemistry of Organic Geminal Di- and Triazides. (United States)

    Häring, Andreas P; Kirsch, Stefan F


    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.

  12. Concept of Green Chemistry-Redesigning Organic Synthesis

    Indian Academy of Sciences (India)

    Home; Journals; Resonance – Journal of Science Education; Volume 13; Issue 11. Concept of Green Chemistry - Redesigning Organic Synthesis. Bharati V Badami. General Article Volume 13 Issue 11 November 2008 pp 1041-1048. Fulltext. Click here to view fulltext PDF. Permanent link:

  13. Ultrasound: A Boon in the Synthesis of Organic Compounds

    Indian Academy of Sciences (India)

    Home; Journals; Resonance – Journal of Science Education; Volume 3; Issue 9. Ultrasound: A Boon in the Synthesis of Organic Compounds. Vasundhara Singh Kanwal Preet Kaur Anupam Khurana G L Kad. General Article Volume 3 Issue 9 September 1998 pp 56-60 ...


    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...

  15. Synthesis of Organic Compounds for Malaria Chemotherapeutic Studies (United States)


    AD__ REPORT NUMBER 10 SYNTHESIS OF ORGANIC COMPOUNDS FOR MALARIA CHEMOTHERAPEUTIC STUDIES SANNUAL PROGRESS REPORT by L • ,C. C. Cheng, Ph.D. Ping-Lu...block number) 8-Aminoquinollnes, Antimalarial Activity, Diastereoisomers, Febrifugine, Furanomycin, Malaria , Malaria Chemotherapeutic Agents...andtilte organic layer were dried over muagnesium sulfate-, evaporastion of ether gavi - a d.)rk brown liquid. ThIAN was distilled at anl oil-bath tow

  16. Earthworm Is a Versatile and Sustainable Biocatalyst for Organic Synthesis (United States)

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


    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

  17. Synthesis of Organics in the Early Solar Nebula (United States)

    Johnson, Natasha M.; Manning, S.; Nuth, J. A., III


    It is unknown what process or processes made the organics that are found or detected in extraterrestrial materials. One process that forms organics are Fischer-Tropsch type (FTT) reactions. Fischer-Tropsch type synthesis produces complex hydrocarbons by hydrogenating carbon monoxide via surface mediated reactions. The products of these reactions have been well-studied using `natural’ catalysts [1] and calculations of the efficiency of FTT synthesis in the Solar Nebula suggest that these types of reactions could make significant contributions to material near three AU [2]. We use FTT synthesis to coat Fe-silicate amorphous grains with organic material to simulate the chemistry in the early Solar Nebula. These coatings are composed of macromolecular organic phases [3]. Previous work also showed that as the grains became coated, Haber-Bosch type reactions took place resulting in nitrogen-bearing organics [4]. Our experiments consist of circulating CO, N2, and H2 gas through Fe- amorphous silicate grains that are maintained at a specific temperature in a closed system. The gases are passed through an FTIR spectrometer and are measured to monitor the reaction progress. Samples are analyzed using FTIR, and GCMS (including pyrolysis) and extraction techniques are used to analyze the organic coatings. These experiments show that these types of reactions are an effective means to produce complex hydrocarbons. We present the analysis of the produced organics (solid and gas phase) and the change in the production rate of several compounds as the grains become coated. Organics generated by this technique could represent the carbonaceous material incorporated in comets and meteorites. References: [1] Hayatsu and Anders 1981. Topics in Current Chemistry 99:1-37. [2] Kress and Tielens 2001. MAPS 36:75-91. [3] Johnson et al. 2004. #1876. 35th LPSC. [4] Hill and Nuth 2003. Astrobiology 3:291-304. This work was supported by a grant from NASA.

  18. Mechanochemical synthesis of small organic molecules

    Directory of Open Access Journals (Sweden)

    Tapas Kumar Achar


    Full Text Available With the growing interest in renewable energy and global warming, it is important to minimize the usage of hazardous chemicals in both academic and industrial research, elimination of waste, and possibly recycle them to obtain better results in greener fashion. The studies under the area of mechanochemistry which cover the grinding chemistry to ball milling, sonication, etc. are certainly of interest to the researchers working on the development of green methodologies. In this review, a collection of examples on recent developments in organic bond formation reactions like carbon–carbon (C–C, carbon–nitrogen (C–N, carbon–oxygen (C–O, carbon–halogen (C–X, etc. is documented. Mechanochemical syntheses of heterocyclic rings, multicomponent reactions and organometallic molecules including their catalytic applications are also highlighted.

  19. Towards waste free organic synthesis using nanostructured hybrid silicas. (United States)

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


    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.

  20. Abiotic tooth enamel (United States)

    Yeom, Bongjun; Sain, Trisha; Lacevic, Naida; Bukharina, Daria; Cha, Sang-Ho; Waas, Anthony M.; Arruda, Ellen M.; Kotov, Nicholas A.


    Tooth enamel comprises parallel microscale and nanoscale ceramic columns or prisms interlaced with a soft protein matrix. This structural motif is unusually consistent across all species from all geological eras. Such invariability—especially when juxtaposed with the diversity of other tissues—suggests the existence of a functional basis. Here we performed ex vivo replication of enamel-inspired columnar nanocomposites by sequential growth of zinc oxide nanowire carpets followed by layer-by-layer deposition of a polymeric matrix around these. We show that the mechanical properties of these nanocomposites, including hardness, are comparable to those of enamel despite the nanocomposites having a smaller hard-phase content. Our abiotic enamels have viscoelastic figures of merit (VFOM) and weight-adjusted VFOM that are similar to, or higher than, those of natural tooth enamels—we achieve values that exceed the traditional materials limits of 0.6 and 0.8, respectively. VFOM values describe resistance to vibrational damage, and our columnar composites demonstrate that light-weight materials of unusually high resistance to structural damage from shocks, environmental vibrations and oscillatory stress can be made using biomimetic design. The previously inaccessible combinations of high stiffness, damping and light weight that we achieve in these layer-by-layer composites are attributed to efficient energy dissipation in the interfacial portion of the organic phase. The in vivo contribution of this interfacial portion to macroscale deformations along the tooth’s normal is maximized when the architecture is columnar, suggesting an evolutionary advantage of the columnar motif in the enamel of living species. We expect our findings to apply to all columnar composites and to lead to the development of high-performance load-bearing materials.

  1. Engineering and Applications of fungal laccases for organic synthesis (United States)

    Kunamneni, Adinarayana; Camarero, Susana; García-Burgos, Carlos; Plou, Francisco J; Ballesteros, Antonio; Alcalde, Miguel


    Laccases are multi-copper containing oxidases (EC, 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. PMID:19019256

  2. Engineering and Applications of fungal laccases for organic synthesis

    Directory of Open Access Journals (Sweden)

    Ballesteros Antonio


    Full Text Available Abstract Laccases are multi-copper containing oxidases (EC, 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.

  3. A novel liquid-phase strategy for organic synthesis using organic ions as soluble supports. (United States)

    Huo, Congde; Chan, Tak Hang


    This critical review describes a new liquid-phase strategy for organic synthesis by using organic ions as soluble supports. Catalysts or reagents or substrates are immobilized onto organic ions. They are generally soluble in polar organic solvents (e.g. CH(3)CN) or ionic liquids but insoluble in non-polar solvents (e.g. ether or hexanes). Their reactions are carried out in homogeneous solution phase with a polar organic solvent or ionic liquid. After the reaction, the ion-supported species can be phase separated through precipitation from the polar organic solvent by the addition of a less polar organic solvent or extraction with organic solvents from ionic liquids. The ion-supported species can therefore be easily recovered and purified from the reaction mixture by simple washings with the less polar solvent. The ion-tagged species can function in the role of a catalyst, or as a reagent, or as the substrate in the synthesis of small molecules or bio-oligomers. Ion-supported catalysts and reagents can usually be recovered and reused with little diminution of activity. Important biooligomers such as peptides, oligosaccharides and oligonucleotides have been synthesized with this method (136 references).

  4. Production of hydroxyl radicals from abiotic oxidation of pyrite by oxygen under circumneutral conditions in the presence of low-molecular-weight organic acids (United States)

    Zhang, Peng; Yuan, Songhu


    Besides acidic environments, pyrite oxidation also occurs in circumneutral environments, such as well-buffered marine and estuarine sediments and salt marshes where low-molecular-weight organic acids (LMWOAs) (e.g., citrate and oxalate) prevail. However, the production of hydroxyl radicals (radOH) from pyrite oxidation by oxygen (O2) in these circumneutral environments is poorly understood. In this study, radOH production was measured during the abiotic oxidation of pyrite by O2 under circumneutral conditions. A pyrite suspension (50 g/L pyrite) that was buffered at pH 6-8 was exposed to air for oxygenation in the dark. Benzoate (20 mM) was added into the suspension to trap radOH. At pH 7, the cumulative radOH reached 7.5 μM within 420 min in the absence of LMWOAs, whereas it increased to 14.8, 12 and 11.2 μM in the presence of 1 mM ethylenediaminotetraacetate, citrate and oxalate, respectively. When the citrate concentration, which serves as a LMWOAs model, was increased from 0.5 to 5 mM, the cumulative radOH increased from 10.3 to 27.3 μM within 420 min at pH 7. With the decrease in pH from 8 to 6, the cumulative radOH increased from 2.1 to 23.3 μM in the absence of LMWOAs, but it increased from 8.8 to 134.9 μM in the presence of 3 mM citrate. The presence of LMWOAs enhanced the radOH production from pyrite oxidation under circumneutral conditions. In the absence of LMOWAs, radOH is produced mostly from the oxidation of adsorbed Fe(II) by O2. In the presence of citrate, radOH production is attributed mainly to the oxidation of Fe(II)-citrate- by O2 and secondarily to the oxidation of H2O on surface-sulfur defects. The acceleration of pyrite oxidation by Fe(III)-citrate increases radOH production. Fe(II)-citrate- is generated mainly from the complexation of adsorbed Fe(II) by citrate and the reduction of Fe(III)-citrate, and the generation is suppressed by the oxidation of adsorbed Fe(II). Fe(III)-citrate is generated predominantly from Fe

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

    KAUST Repository

    Qiu, Shilun


    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.

  6. Electrical energy sources for organic synthesis on the early earth (United States)

    Chyba, Christopher; Sagan, Carl


    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.

  7. Synthesis and postmodification of functionally relevant organically modified silica particles (United States)

    Brozek, Eric

    This thesis describes the synthesis and properties of organically modified silica (ORMOSIL) particles with possible applications in the field of drug delivery. Nanoparticle drug delivery methods take advantage of the unique physical properties of nanoscale architecture to deliver a large payload of drug to a targeted site. They are highly porous, contain many organic functionalities for covalent attachment, and their surfaces can be functionalized. A particle-based approach allows for the delivery of a large and localized payload in a single package. Initial study focused on the generation of submicron organically modified silica particles containing boron. This involved the synthesis of vinyl-enriched silica particles and the postmodification of the vinyl functionalities throughout the particle body. Hydroboration and bromination of the vinyl functionalities showed for the first time that the organic functionalities of ORMOSIL particles could be significantly modified. Next, new organically modified silica particle types were developed. These new particle types incorporated unique organic functionalities that may undergo additional functionalization. Organic functionalities included alkenyl-, cyano-, mercapto-, and isocyanto- throughout the particle body. The different organic functionalities were then modified to demonstrate their reactivity. Finally, a particle containing nuclei suitable for neutron capture therapy, a fluorescent tag, and targeting ligand was synthesized. Boron was the active nuclei, fluorescein was the fluorescent label, useful for in vitro studies, and folic acid is a broad field targeting ligand, useful in targeting a variety of cancer types. The particle containing the three unique motifs underwent early stages of in vitro studies against the OVCAR-3 cell line. This thesis has considerably advanced the field of ORMOSIL chemistry through the development and modification of new ORMOSIL products. While initial efforts were geared toward the

  8. Greener and Sustainable Trends in Synthesis of Organics and ... (United States)

    Trends in greener and sustainable process development during the past 25 years are abridged involving the use of alternate energy inputs (mechanochemistry, ultrasound- or microwave irradiation), photochemistry, and greener reaction media as applied to synthesis of organics and nanomaterials. In the organic synthesis arena, examples comprise assembly of heterocyclic compounds, coupling and a variety of other name reactions catalyzed by basic water or recyclable magnetic nanocatalysts. Generation of nanoparticles benefits from the biomimetic approaches where vitamins, sugars, and plant polyphenols, including agricultural waste residues, can serve as reducing and capping agents. Metal nanocatalysts (Pd, Au, Ag, Ni, Ru, Ce, Cu, etc.) immobilized on biodegradable supports such as cellulose and chitosan, or on recyclable magnetic ferrites via ligands, namely dopamine or glutathione, are receiving special attention. These strategic approaches attempt to address most of the Green Chemistry Principles while producing functional chemicals with utmost level of waste minimization. Feature article for celebration of 25 years of Green Chemistry on invitation from American Chemical Society (ACS) journal, ACS Sustainable Chemistry & Engineering.

  9. Recyclable Nanostructured Catalytic Systems in Modern Environmentally Friendly Organic Synthesis

    Directory of Open Access Journals (Sweden)

    Irina Beletskaya


    Full Text Available Modern chemical synthesis makes heavy use of different types of catalytic systems: homogeneous, heterogeneous and nano-sized. The latter – nano-sized catalysts – have given rise in the 21st century to a rapidly developing area of research encompassing several prospects and opportunities for new technologies. Catalytic reactions ensure high regio- and stereoselectivity of chemical transformations, as well as better yields and milder reaction conditions. In recent years several novel catalytic systems were developed for selective formation of carbon-heteroatom and carbon-carbon bonds. This review presents the achievements of our team in our studies on various types of catalysts containing metal nanoparticles: palladium-containing diblock copolymer micelles; soluble palladium-containing polymers; metallides on a support; polymeric metal salts and oxides; and, in addition, metal-free organic catalysts based on soluble polymers acting as nanoreactors. Representative examples are given and discussed in light of possible applications to solve important problems in modern organic synthesis.

  10. Synthesis of Two Local Anesthetics from Toluene: An Organic Multistep Synthesis in a Project-Oriented Laboratory Course (United States)

    Demare, Patricia; Regla, Ignacio


    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…

  11. 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 (United States)

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


    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.

  12. 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 (United States)

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


    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 formed 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.

  13. The Stable Isotope Fractionation of Abiotic Reactions: A Benchmark in the Detection of Life (United States)

    Summers, David P.


    mil to as low as -60 % (potentially comparable to that which accompanies the biosynthesis of organic matter). We need to understand what kind of fractionations are observed with reactions under the non-reducing or mildly reducing conditions now thought to be present on the early Earth. While nitrogen is receiving increased attention as a tool for these kinds of analyses, almost nothing is known about the isotope fractionation that one would expect for abiotic sources of fixed/reduced nitrogen. This project will measure the fixation from a series of abiotic reactions that may have been present on the early Earth (and other terrestrial planets) and produced organic material that could have ended up in the rock record. The work will look at a number of reactions, under a non- reducing, or mildly reducing, atmosphere, covering sources of prebiotic organic C & N from shock heating, to photochemistry, to hydrothermal reactions. Some reactions that we plan to study are; Shock heating of a non-reducing atmosphere to produce CO and NO (in collaboration with Chris McKay), formation of formaldehyde (and related compounds) from COY the formation of ammonia from nitrogen oxides (ultimately from NO) by ferrous iron reduction, and the hydrothermal synthesis of compounds including the hydrocarboxylation/hydrocarbonylation reaction (in collaboration with George Cody), reactions of oxalate to form hydrocarbons and other oxygenated compounds and the formation of lipids from oxalic/formic acid (in collaboration with Tom McCollom), and reactions of carbon monoxide & carbon dioxide with N2, ammonia or nitritehitrate to form hydrogen cyanide, nitriles, ammonia/amines and nitrous

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

    Touaibia, Mohamed; Guay, Michel


    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…

  15. Synthesis of the DDT metabolite 2,4-dichloro-1-[2-chloro-1-(4-chlorophenyl)ethenyl]benzene (o-Cl-DDMU) and its detection in abiotic and biotic samples. (United States)

    Gallistl, Christoph; Proctor, Katie; Bader, Korinna; Vetter, Walter


    Technical dichlorodiphenyltrichloroethane (DDT) has been used worldwide as a pesticide since the beginning of the 1940s. Due to its persistence, DDT residues are still ubiquitously distributed in the environment. Photochemical UV degradation has been shown to be a potent degradation path for DDT and most of the resulting photoproducts have been identified up to now. Nevertheless, in 2012, a new DDT metabolite, most likely formed photochemically from DDE, was detected in ray liver samples from Brazil, an area which is highly contaminated with DDT. This study includes photochemical generation, chemical synthesis and isolation of this compound which was verified to consist of both cis- and trans-2,4-dichloro-1-[2-chloro-1-(4-chlorophenyl)ethenyl]benzene. Both stereoisomers were resolved by gas chromatography on a polar capillary column and detected in more than 60 biotic (e.g. marine mammals, birds, human milk) and abiotic samples (fat deposits in kitchen hoods) from different areas all over the world. The stereoisomer distribution and concentrations (0.3-3.9% relative to corresponding 1,1-dichloro-2,2-bis(p-chlorophenyl) ethane (p,p'-DDE) levels) were determined by means of the synthesized analytical standard, indicating the widespread occurrence of this compound as an additional minor metabolite of DDT.

  16. Methane clumped isotopes in the Songliao Basin (China): New insights into abiotic vs. biotic hydrocarbon formation (United States)

    Shuai, Yanhua; Etiope, Giuseppe; Zhang, Shuichang; Douglas, Peter M. J.; Huang, Ling; Eiler, John M.


    Abiotic hydrocarbon gas, typically generated in serpentinized ultramafic rocks and crystalline shields, has important implications for the deep biosphere, petroleum systems, the carbon cycle and astrobiology. Distinguishing abiotic gas (produced by chemical reactions like Sabatier synthesis) from biotic gas (produced from degradation of organic matter or microbial activity) is sometimes challenging because their isotopic and molecular composition may overlap. Abiotic gas has been recognized in numerous locations on the Earth, although there are no confirmed instances where it is the dominant source of commercially valuable quantities in reservoir rocks. The deep hydrocarbon reservoirs of the Xujiaweizi Depression in the Songliao Basin (China) have been considered to host significant amounts of abiotic methane. Here we report methane clumped-isotope values (Δ18) and the isotopic composition of C1-C3 alkanes, CO2 and helium of five gas samples collected from those Xujiaweizi deep reservoirs. Some geochemical features of these samples resemble previously suggested identifiers of abiotic gas (13C-enriched CH4; decrease in 13C/12C ratio with increasing carbon number for the C1-C4 alkanes; abundant, apparently non-biogenic CO2; and mantle-derived helium). However, combining these constraints with new measurements of the clumped-isotope composition of methane and careful consideration of the geological context, suggests that the Xujiaweizi depression gas is dominantly, if not exclusively, thermogenic and derived from over-mature source rocks, i.e., from catagenesis of buried organic matter at high temperatures. Methane formation temperatures suggested by clumped-isotopes (167-213 °C) are lower than magmatic gas generation processes and consistent with the maturity of local source rocks. Also, there are no geological conditions (e.g., serpentinized ultramafic rocks) that may lead to high production of H2 and thus abiotic production of CH4 via CO2 reduction. We propose

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

    DEFF Research Database (Denmark)

    Viart, Helene Marie-France

    In a desire to explore various areas of syntheticorganic chemistry, different projects have been carried out, and each of the four following chapterswill describe the workcarried out on each of them. The first three chapters are related in someextent and treat the synthesis and biochemical...... of the epidermis of land plants. The enzyme responsible for the polymerization (CD1), as well as its substrate, has been identified, and the role of the enzyme has been demonstrated by its activity on the synthetic dihydroxyacylglycerol. Finally, the last chapter differs greatly from the first three by its focus......: 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....

  18. Colloidal-sized metal-organic frameworks: synthesis and applications. (United States)

    Sindoro, Melinda; Yanai, Nobuhiro; Jee, Ah-Young; Granick, Steve


    Colloidal metal-organic frameworks (CMOFs), nanoporous colloidal-sized crystals that are uniform in both size and polyhedral shape, are crystals composed of metal ions and organic bridging ligands, which can be used as building blocks for self-assembly in organic and aqueous liquids. They stand in contrast to conventional metal-organic frameworks (MOFs), which scientists normally study in the form of bulk crystalline powders. However, powder MOFs generally have random crystal size and shape and therefore do not possess either a definite mutual arrangement with adjacent particles or uniformity. CMOFs do have this quality, which can be important in vital uptake and release kinetics. In this Account, we present the diverse methods of synthesis, pore chemistry control, surface modification, and assembly techniques of CMOFs. In addition, we survey recent achievements and future applications in this emerging field. There is potential for a paradigm shift, away from using just bulk crystalline powders, towards using particles whose size and shape are regulated. The concept of colloidal MOFs takes into account that nanoporous MOFs, conventionally prepared in the form of bulk crystalline powders with random crystal size, shape, and orientation, may also form colloidal-sized objects with uniform size and morphology. Furthermore, the traditional MOF functions that depend on porosity present additional control over those MOF functions that depend on pore interactions. They also can enable controlled spatial arrangements between neighboring particles. To begin, we discuss progress regarding synthesis of MOF nano- and microcrystals whose crystal size and shape are well regulated. Next, we review the methods to modify the surfaces with dye molecules and polymers. Dyes are useful when seeking to observe nonluminescent CMOFs in situ by optical microscopy, while polymers are useful to tune their interparticle interactions. Third, we discuss criteria to assess the stability of CMOFs

  19. Genome-wide analysis of the grapevine stilbene synthase multigenic family: genomic organization and expression profiles upon biotic and abiotic stresses

    Directory of Open Access Journals (Sweden)

    Vannozzi Alessandro


    Full Text Available Abstract Background Plant stilbenes are a small group of phenylpropanoids, which have been detected in at least 72 unrelated plant species and accumulate in response to biotic and abiotic stresses such as infection, wounding, UV-C exposure and treatment with chemicals. Stilbenes are formed via the phenylalanine/polymalonate-route, the last step of which is catalyzed by the enzyme stilbene synthase (STS, a type III polyketide synthase (PKS. Stilbene synthases are closely related to chalcone synthases (CHS, the key enzymes of the flavonoid pathway, as illustrated by the fact that both enzymes share the same substrates. To date, STSs have been cloned from peanut, pine, sorghum and grapevine, the only stilbene-producing fruiting-plant for which the entire genome has been sequenced. Apart from sorghum, STS genes appear to exist as a family of closely related genes in these other plant species. Results In this study a complete characterization of the STS multigenic family in grapevine has been performed, commencing with the identification, annotation and phylogenetic analysis of all members and integration of this information with a comprehensive set of gene expression analyses including healthy tissues at differential developmental stages and in leaves exposed to both biotic (downy mildew infection and abiotic (wounding and UV-C exposure stresses. At least thirty-three full length sequences encoding VvSTS genes were identified, which, based on predicted amino acid sequences, cluster in 3 principal groups designated A, B and C. The majority of VvSTS genes cluster in groups B and C and are located on chr16 whereas the few gene family members in group A are found on chr10. Microarray and mRNA-seq expression analyses revealed different patterns of transcript accumulation between the different groups of VvSTS family members and between VvSTSs and VvCHSs. Indeed, under certain conditions the transcriptional response of VvSTS and VvCHS genes appears to be

  20. Synthesis of 10-Ethyl Flavin: A Multistep Synthesis Organic Chemistry Laboratory Experiment for Upper-Division Undergraduate Students (United States)

    Sichula, Vincent A.


    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…

  1. 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.


    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.

  2. Modern separation techniques for the efficient workup in organic synthesis. (United States)

    Tzschucke, Carl Christoph; Markert, Christian; Bannwarth, Willi; Roller, Sebastian; Hebel, André; Haag, Rainer


    The shift of paradigm in combinatorial chemistry, from large compound libraries (of mixtures) on a small scale towards defined compound libraries where each compound is prepared in an individual well, has stimulated the search for alternative separation approaches. The key to a rapid and efficient synthesis is not only the parallel arrangement of reactions, but simple work-up procedures so as to circumvent time-consuming and laborious purification steps. During the initial development stages of combinatorial synthesis it was believed that rational synthesis of individual compounds could only be achieved by solid-phase strategies. However, there are a number of problems in solid-phase chemistry: most notably there is the need for a suitable linker unit, the limitation of the reaction conditions to certain solvents and reagents, and the heterogeneous reaction conditions. Further disadvantages are: the moderate loading capacities of the polymeric support and the limited stability of the solid support. In the last few years several new separation techniques have been developed. Depending on the chemical problem or the class of compounds to be prepared, one can choose from a whole array of different approaches. Most of these modern separation approaches rely on solution-phase chemistry, even though some of them use solid-phase resins as tools (for example, as scavengers). Several of these separation techniques are based on liquid-liquid phase separation, including ionic liquids, fluorous phases, and supercritical solvents. Besides being benign with respect to their environmental aspects, they also show a number of advantages with respect to the work-up procedures of organic reactions as well as simplicity in the isolation of products. Another set of separation strategies involves polymeric supports (for example, as scavengers or for cyclative cleavage), either as solid phases or as soluble polymeric supports. In contrast to solid-phase resins, soluble polymeric supports

  3. Synthesis of Dehydrobenzoannulene-Based Covalent Organic Frameworks (United States)

    Baldwin, Luke Adam

    Our group is interested in covalent organic frameworks (COFs), a class of highly crystalline, well-ordered 2D and 3D polymers with predictable pore sizes, photophysical properties, and well-defined structures. Other materials that interested our group include graphyne and graphdiyne, as well as substructures of these carbon allotropes. Our research centers on the design and synthesis of novel, functional, 2D and 3D COFs with macrocycles for post-synthetic alterations Specifically, the incorporation of DBA[12] and DBA[18] macrocycles into crystalline materials intrigued our group. We first started by synthesizing two DBA based COFs with a mixture of alternating triangular and hexagonal pores using a C2-symmetric diboronic acid linker. After synthesis we found that these COFs were extremely thermally stable, highly porous, and crystalline. Incorporation of DBA into the polymers also allowed for highly fluorescent materials that had micropores (0.4 to 0.5 nm) from the DBA units, and mesopores (3.2 to 3.6 nm) from the hexagonal pore of the COF. Turning our attention to three component COFs we reported the synthesis of three novel COFs that contained a homogeneous and heterogeneous distribution of DBA vertex units. The COFs were synthesized using different ratios of DBA[12], DBA[18], and diboronic acid to yield three COFs with high crystallinity, and interesting luminescent properties. This protocol showed that the pore size of COFs can be altered by incorporating different mixtures of DBA vertex units in the polymer. After our success in 2D COFs we turned our attention to constructing metalated three-dimensional COFs. We synthesized a highly porous DBA based 3D COF with a record high surface area (SABET = 5083 m2g -1) and record low density (0.13 g/cm3) for a COF material. Metalation of the DBA-3D COF with Ni resulted in minimal reduction to the surface area, and retention of crystallinity. We explored these COFs for the uptake of ethane and ethylene gas to determine

  4. Confinement Effects on Carbon Dioxide Methanation: A Novel Mechanism for Abiotic Methane Formation

    National Research Council Canada - National Science Library

    Thu Le; Alberto Striolo; C Heath Turner; David R Cole


    (ProQuest: ... denotes formulae and/or non-USASCII text omitted; see image) An important scientific debate focuses on the possibility of abiotic synthesis of hydrocarbons during oceanic crust-seawater interactions...

  5. Selective organic synthesis over metal cation-exchanged clay catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Tateiwa, J.; Uemura, S. [Kyoto University, Kyoto (Japan)


    Results of recent studies conducted by the authors are reviewed on the use, as catalysts, of metal cation-exchanged montmorillonite (M{sup n+}-mont), a modified natural clay with a layer structure, and metal cation-exchanged fluor-tetrasilicic mica (M{sup n+}-TSM), a synthetic clay with a layer structure, for the following organic synthesis: (1) Friedel-Crafts alkylation of phenol with 4-hydroxybutan-2-one to produce 4-(4-hydroxyphenyl)butan-2-one (raspberry ketone), (2) rearrangement of alkyl phenyl ethers to corresponding alkylphenols, (3) aromatic alkylation of phenol with aldehydes and ketones to produce corresponding gem-bis(hydroxyphenyl)alkanes (bisphenols) and alkylphenols, respectively, (4) a facile and an almost quantitative substrate-selective acetalization, (5) alkane oxidation with aqueous tert-butyl hydroperoxide, (6) Prins reaction of styrenes with aldehydes using clay as a Bronsted acid, and (7) inter-and intra-molecular carbonyl-ene reaction using clay as a Lewis acid in condition similar to that of Prins reaction. In almost all cases, the clay catalysts could be regenerated and reused several times, after filtration, washing and drying. 42 refs., 20 figs., 3 tabs.

  6. Some recent work on prebiological synthesis of organic compounds. (United States)

    Ponnamperuma, C.


    Origin of constituents of nucleic acid and protein molecules, noting biological molecules synthesis under conditions similar to those prevailing in prebiotic Earth, following Oparin-Haldane hypothesis

  7. Abiotic loss of chemicals in soil

    Energy Technology Data Exchange (ETDEWEB)

    Erickson, D.C.; Spaniel, K.; Loehr, R.C. (Univ. of Texas, Austin (USA))

    A laboratory study was conducted to evaluate the abiotic losses of organics in soil. 2,3- and 2,5-dichlorophenol were added to microcosms containing soil treated either by autoclaving or gamma irradiation or incubated under anoxic conditions. Biologically active aerobic microcosms were used as controls. Losses of the compounds were monitored using gas chromatography. Significant losses were observed in both the autoclaved and irradiated soils. Loss rates in the autoclaved soils were lowest; losses were greatest in the biologically active soils. Anoxic conditions slowed but did not stop the losses. Autoclaving and radiation appeared to increase the sorptive capacity of the soil. The study stresses the difficulty of achieving sterile conditions in soils, even when sound sterilization methods are used by competent analysts. Studies that report information about sterile conditions and abiotic losses of chemicals in soils should check for, and not presume, sterility in any tests that are conducted.

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

    Directory of Open Access Journals (Sweden)

    Nina Kann


    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.

  9. A Long Chain Alcohol as Support in Solid Phase Organic Synthesis

    NARCIS (Netherlands)

    Nurlela, Yeni; Minnaard, Adrian J.; Achmad, Sadijah; Wahyuningrum, Deana

    The solid phase synthesis is a method by which organic compound synthesis are performed on a support. With this method, the purification can be carried out easily by simple filtration and washing procedures. Long-chain alcohol (C-100 alcohol) can be used as a support because of its insolubility in

  10. Carbon Isotope Characterization of Organic Intermediaries in Hydrothermal Hydrocarbon Synthesis by Pyrolysis-GC-MS-C-IRMS (United States)

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


    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

  11. Designing cooperatively folded abiotic uni- and multimolecular helix bundles (United States)

    de, Soumen; Chi, Bo; Granier, Thierry; Qi, Ting; Maurizot, Victor; Huc, Ivan


    Abiotic foldamers, that is foldamers that have backbones chemically remote from peptidic and nucleotidic skeletons, may give access to shapes and functions different to those of peptides and nucleotides. However, design methodologies towards abiotic tertiary and quaternary structures are yet to be developed. Here we report rationally designed interactional patterns to guide the folding and assembly of abiotic helix bundles. Computational design facilitated the introduction of hydrogen-bonding functionalities at defined locations on the aromatic amide backbones that promote cooperative folding into helix-turn-helix motifs in organic solvents. The hydrogen-bond-directed aggregation of helices not linked by a turn unit produced several thermodynamically and kinetically stable homochiral dimeric and trimeric bundles with structures that are distinct from the designed helix-turn-helix. Relative helix orientation within the bundles may be changed from parallel to tilted on subtle solvent variations. Altogether, these results prefigure the richness and uniqueness of abiotic tertiary structure behaviour.

  12. Reactive organometallics from organotellurides: application in organic synthesis

    Energy Technology Data Exchange (ETDEWEB)

    Princival, Jefferson L.; Santos, Alcindo A. dos; Comasseto, Joao V., E-mail: jvcomass@iq.usp.b [Universidade de Sao Paulo (USP), SP (Brazil). Inst. de Quimica


    In this paper the preparation of reactive organometallics starting from organotellurides is reviewed. The application of the reactive organometallics prepared in this way in the synthesis of bioactive compounds is commented. (author)

  13. Design and synthesis of organic semiconductors for use in organic field effect transistors (United States)

    Murphy, Amanda Ruth

    In the past ten years, much progress has been made in producing organic semiconductors with properties that rival amorphous silicon. Organic semiconductors are sought for low-cost or large-area electronic devices such as organic field-effect transistors (OFETs), light-emitting diodes (OLEDs), photovoltaic cells, sensors, and radio frequency identification (RFID) tags. Low temperature processing options and the ductility of organic materials also allow flexible plastics or fabrics to be used as substrates. However, the majority of the newly developed materials are insoluble requiring the use of thermal evaporation to obtain thin films. In order for these organic semiconductors to compete as 'low cost' alternatives to silicon, manufacturers must be able to use large-area, continuous, reel-to-reel methods for production, which would likely involve the solution-based deposition methods such as spin coating, stamping, or printing. Therefore, our work has focused on methods for solubilizing and controlling the self-assembly of conjugated oligomers in order to maximize the semiconducting properties from solution-based processes. Chapter 1 gives a general overview of charge transfer in organic semiconductors, and describes how devices are fabricated and tested. An extensive review of the literature on solution processed p- and n-type oligomers is also given. Chapter 2 and 3 discuss our initial attempts to produce soluble oligothiophenes capable of self-assembly. Chapter 2 focuses on beta-functionalized heptathiophene oligomers, while Chapter 3 deals with (x-(x'-substituted oligothiophene derivatives. A synthetic method for incorporating thermally removable solubilizing groups into organic semiconductors is outlined in Chapter 4, and demonstrated using a sexithiophene oligomer. The synthesis, chemical characterization, as well as an in-depth characterization of solution-processed films of this oligomer using AFM and NEXAFS spectroscopy is given. This theme is carried over

  14. Surface chemistry allows for abiotic precipitation of dolomite at low temperature. (United States)

    Roberts, Jennifer A; Kenward, Paul A; Fowle, David A; Goldstein, Robert H; González, Luis A; Moore, David S


    Although the mineral dolomite is abundant in ancient low-temperature sedimentary systems, it is scarce in modern systems below 50 °C. Chemical mechanism(s) enhancing its formation remain an enigma because abiotic dolomite has been challenging to synthesize at low temperature in laboratory settings. Microbial enhancement of dolomite precipitation at low temperature has been reported; however, it is still unclear exactly how microorganisms influence reaction kinetics. Here we document the abiotic synthesis of low-temperature dolomite in laboratory experiments and constrain possible mechanisms for dolomite formation. Ancient and modern seawater solution compositions, with identical pH and pCO2, were used to precipitate an ordered, stoichiometric dolomite phase at 30 °C in as few as 20 d. Mg-rich phases nucleate exclusively on carboxylated polystyrene spheres along with calcite, whereas aragonite forms in solution via homogeneous nucleation. We infer that Mg ions are complexed and dewatered by surface-bound carboxyl groups, thus decreasing the energy required for carbonation. These results indicate that natural surfaces, including organic matter and microbial biomass, possessing a high density of carboxyl groups may be a mechanism by which ordered dolomite nuclei form. Although environments rich in organic matter may be of interest, our data suggest that sharp biogeochemical interfaces that promote microbial death, as well as those with high salinity may, in part, control carboxyl-group density on organic carbon surfaces, consistent with origin of dolomites from microbial biofilms, as well as hypersaline and mixing zone environments.

  15. Eco-friendly Synthesis of Organics and Nanomaterials ... (United States)

    The presentation summarizes our recent activity in chemical synthesis involving benign alternatives, such as the use of supported reagents, and greener reaction medium in aqueous or solvent-free conditions.1 The synthesis of heterocyclic compounds, coupling reactions, and a variety of name reactions2 are the primary beneficiaries as exemplified by the synthesis of N-aryl azacycloalkanes, isoindoles, and dihydropyrazoles, 1,3,4-oxadiazoles, 1,3,4-thiadiazoles, 1,3-dioxanes, pyrazoles, catalyzed by basic water or polystyrene sulfonic acid (PSSA) in conjunction with microwave (MW) irradiation.2 Vitamins B1, B2, C, and tea and wine polyphenols which function both as reducing and capping agents, provide extremely simple, one-pot, green synthetic methods to bulk quantities of nanomaterials in water.3a Shape-controlled synthesis of noble nanostructures via MW-assisted spontaneous reduction of noble metal salts using sugars will be presented.3b A general method has been developed for the cross-linking reaction of poly (vinyl alcohol) (PVA) with metallic systems; bimetallic systems,3c and SWNT, MWNT, and C-60.3d The strategy is extended to the formation of biodegradable carboxymethylcellulose (CMC) composite films with noble nanometals;3e such metal decoration and alignment of carbon nanotubes in CMC is possible using MW approach3f which also enables the shape-controlled bulk synthesis of Ag and Fe nanorods in poly (ethylene glycol).3g MW hydrothermal process delivers m

  16. Abiotic and Biotic Formation of Amino Acids in the Enceladus Ocean. (United States)

    Steel, Elliot L; Davila, Alfonso; McKay, Christopher P


    The active plume at Enceladus' south pole makes the indirect sampling of its global ocean possible. The partially resolved chemistry of the plume, which points to conditions that are seemingly compatible with life, has made orbital sampling missions a priority. We present a conceptual model of energy flux, hydrothermal H 2 production, and both abiotic and biotic production of amino acids. Based on the energy flux observed at the south pole and the inferred internal hydrothermal activity, we estimate an H 2 production of 0.6-34 mol/s from serpentinization, sufficient to sustain abiotic and biotic amino acid synthesis of 1.6-87 and 1-44 g/s, respectively. Two-dimensional (2D) numerical simulations of the hydrothermal vent suggest that the vent fluids could reach the ice-water boundary in less than 11-55 days for a 50 km deep ocean diluted by ambient ocean water 10 to 1. Concentrations of glycine, alanine, α-amino isobutyric acid, and glutamic acid in the plume and in the ambient ocean could all be above 0.01 μM just due to abiotic production. Biological synthesis, if occurring, could produce a maximum of 90 μM concentrations of amino acids based on a methanogenic ecosystem consuming H 2 and CO 2 . Racemization timescales in the ocean are short compared with production timescales. Thus, no enantiomeric excess is expected in the ambient ocean, and if biology is present, enantiomeric excess at the vent fluids is expected to be less than 10% in the plume. From vent H 2 concentrations of 7.8 mM (e.g., Lost City) and assuming complete H 2 use and conversion to chemical energy by methanogens, cell production is estimated. Annual biomass production in the methanogenic-based biology model is 4 × 10 4 -2 × 10 6 kg/year. This corresponds to cell concentrations ∼10 9 cells/cm 3 in the vents and ∼10 8 cells/cm 3 in the plume, and when diluted into the ambient ocean, we predict cell concentrations of 80-4250 cells/cm 3 . Key Words: Abiotic organic

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

    Directory of Open Access Journals (Sweden)

    Bernd eZechmann


    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.

  18. Organic Synthesis under Solvent-free Condition. An Environmentally ...

    Indian Academy of Sciences (India)

    of research is organosilicon chemistry with particular attention to developing new synthetic procedures and reagents, and studying the reaction mechanisms. Part 1 appeared in Resonance,. VoLl, No.lO, pp. 59-68, 2002. Keywords. Sunlight, photochemistry, chiral products, inclusion complexes, stereoselective synthesis, sol ...

  19. Solid-supported reagents for multi-step organic synthesis: preparation and application. (United States)

    Ley, S V; Baxendale, Ian R; Brusotti, G; Caldarelli, M; Massi, A; Nesi, M


    Since the early days of combinatorial chemistry solid-phase organic synthesis has been the method of choice for the production of large libraries. Solution-phase synthesis is again gaining importance especially for the synthesis of parallel arrays of smaller, focussed libraries containing single compounds with high degrees of purity. In the field of solution-phase library generation, the use of solid-supported reagents, catalysts and scavengers is emerging as a leading strategy, combining the advantages of both solid-phase organic synthesis (e.g. allowing the employment of an excess of reagent without the need for additional purification steps) and solution-phase chemistry (e.g. the ease of monitoring the progress of the reactions by applying LC-MS, TLC or standard NMR techniques). An account of some of the most recent advances in this area of research will be presented.

  20. Template directed synthesis of highly organized functional biomimetic silica nanostructures


    Kind, Lucy


    Silica is an important mineral in technological and biological applications. Many protocols have been developed for the synthesis of complex silica architectures. Most prominent is the silicification approach, where polymers build up the templates for the revealed polymer/silica structures. The current thesis demonstrates that star-shaped polymers and block copolymers are efficient templates for the fabrication of silica particles with spherical or raspberry-like morphology....

  1. Synthesis of the Commercial Fragrance Compound Ethyl 6-Acetoxyhexanoate: A Multistep Ester Experiment for the Second-Year Organic Laboratory (United States)

    McCullagh, James V.; Hirakis, Sophia P.


    This synthesis of ethyl 6-acetoxyhexanoate (Berryflor) is designed as an experiment for use in a second-year organic chemistry course focusing on the synthesis and reaction of esters. The compound is described as having a raspberry-like odor with jasmine and anise aspects. A two-step procedure for its synthesis beginning with inexpensive…

  2. Cyclodextrin-Catalyzed Organic Synthesis: Reactions, Mechanisms, and Applications

    Directory of Open Access Journals (Sweden)

    Chang Cai Bai


    Full Text Available Cyclodextrins are well-known macrocyclic oligosaccharides that consist of α-(1,4 linked glucose units and have been widely used as artificial enzymes, chiral separators, chemical sensors, and drug excipients, owing to their hydrophobic and chiral interiors. Due to their remarkable inclusion capabilities with small organic molecules, more recent interests focus on organic reactions catalyzed by cyclodextrins. This contribution outlines the current progress in cyclodextrin-catalyzed organic reactions. Particular emphases are given to the organic reaction mechanisms and their applications. In the end, the future directions of research in this field are proposed.

  3. Prebiotic organic matter - Possible pathways for synthesis in a geological context (United States)

    Chang, S.


    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.

  4. Proteoglycan synthesis and Golgi organization in polarized epithelial cells. (United States)

    Dick, Gunnar; Akslen-Hoel, Linn K; Grøndahl, Frøy; Kjos, Ingrid; Prydz, Kristian


    A large number of complex glycosylation mechanisms take place in the Golgi apparatus. In epithelial cells, glycosylated protein molecules are transported to both the apical and the basolateral surface domains. Although the prevailing view is that the Golgi apparatus provides the same lumenal environment for glycosylation of apical and basolateral cargo proteins, there are indications that proteoglycans destined for the two opposite epithelial surfaces are exposed to different conditions in transit through the Golgi apparatus. We will here review data relating proteoglycan and glycoprotein synthesis to characteristics of the apical and basolateral secretory pathways in epithelial cells.

  5. 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.


    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.

  6. Studies on the use of haloperoxidases in organic synthesis

    NARCIS (Netherlands)

    Franssen, M.C.R.


    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

  7. A new metalation complex for organic synthesis and polymerization reactions (United States)

    Hirshfield, S. M.


    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.

  8. Crystalline metal-organic frameworks (MOFs): synthesis, structure and function. (United States)

    Dey, Chandan; Kundu, Tanay; Biswal, Bishnu P; Mallick, Arijit; Banerjee, Rahul


    Metal-organic frameworks (MOFs) are a class of hybrid network supramolecular solid materials comprised of organized organic linkers and metal cations. They can display enormously high surface areas with tunable pore size and functionality, and can be used as hosts for a range of guest molecules. Since their discovery, MOFs have experienced widespread exploration for their applications in gas storage, drug delivery and sensing. This article covers general and modern synthetic strategies to prepare MOFs, and discusses their structural diversity and properties with respect to application perspectives.

  9. Synthesis of refractory organic matter in the ionized gas phase of the solar nebula. (United States)

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


    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.

  10. Novel Metal Organic Framework Synthesis for Spacecraft Oxygen Capture Project (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...

  11. Synthesis of ordered carbonaceous frameworks from organic crystals. (United States)

    Nishihara, Hirotomo; Hirota, Tetsuya; Matsuura, Kenta; Ohwada, Mao; Hoshino, Norihisa; Akutagawa, Tomoyuki; Higuchi, Takeshi; Jinnai, Hiroshi; Koseki, Yoshitaka; Kasai, Hitoshi; Matsuo, Yoshiaki; Maruyama, Jun; Hayasaka, Yuichiro; Konaka, Hisashi; Yamada, Yasuhiro; Yamaguchi, Shingi; Kamiya, Kazuhide; Kamimura, Takuya; Nobukuni, Hirofumi; Tani, Fumito


    Despite recent advances in the carbonization of organic crystalline solids like metal-organic frameworks or supramolecular frameworks, it has been challenging to convert crystalline organic solids into ordered carbonaceous frameworks. Herein, we report a route to attaining such ordered frameworks via the carbonization of an organic crystal of a Ni-containing cyclic porphyrin dimer (Ni2-CPDPy). This dimer comprises two Ni-porphyrins linked by two butadiyne (diacetylene) moieties through phenyl groups. The Ni2-CPDPy crystal is thermally converted into a crystalline covalent-organic framework at 581 K and is further converted into ordered carbonaceous frameworks equipped with electrical conductivity by subsequent carbonization at 873-1073 K. In addition, the porphyrin's Ni-N4 unit is also well retained and embedded in the final framework. The resulting ordered carbonaceous frameworks exhibit an intermediate structure, between organic-based frameworks and carbon materials, with advantageous electrocatalysis. This principle enables the chemical molecular-level structural design of three-dimensional carbonaceous frameworks.Carbon-based materials are promising alternatives to noble metal catalysts, but their structures are typically disordered and difficult to control. Here, the authors obtain ordered carbonaceous frameworks with advantageous electrocatalytic properties via the carbonization of nickel-containing porphyrin dimer networks.

  12. Proton-Coupled Electron Transfer in Organic Synthesis: Fundamentals, Applications, and Opportunities (United States)

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


    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 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

  13. Radiation induced synthesis of silver nano-shells formed onto organic micelles

    Energy Technology Data Exchange (ETDEWEB)

    Remita, S. [Paris-5 Univ., (CNRS UMR 8601), Lab. de Chimie et Biochimie Pharmacologiques et Toxicologiques, 75 - Paris (France); Remita, S.; Fontaine, P.; Goldmann, M. [Paris-6 et 7 Univ., (CNRS, UMR 7588), Institut des NanoSciences de Paris, 75 - Paris (France); Fontaine, P.; Muller, F.; Goldmann, M. [Paris-11 Univ., Lab. pour l' Utilisation du Rayonnement Electromagnetique (LURE), (CNRS-CEA-MDR, UMR 130), Centre Universitaire Paris Sud, 91 - Orsay (France); Rochas, C. [Universite Joseph-Fourier, Lab. de Spectrometrie Physique (UJF-CNRS-INPG, UMR 5588), 38 (France)


    Synthesis of metal nano-shells around organic micelles is achieved through radiolysis of aqueous solutions of surfactant self-assembled in spherical micelles and metal ions. The formation of the metal nano-shells is evidenced by UV-visible spectroscopy and Small Angle X-ray Scattering. (authors)

  14. Modulated synthesis of zirconium-metal organic framework (Zr-MOF) for hydrogen storage applications

    CSIR Research Space (South Africa)

    Ren, Jianwei


    Full Text Available A modulated synthesis of Zr-metal organic framework (Zr-MOF) with improved ease of handling and decreased reaction time is reported to yield highly crystalline Zr-MOF with well-defined octahedral shaped crystals for practical hydrogen storage...

  15. 2005 Nobel Prize in Chemistry: Development of the Olefin Metathesis Method in Organic Synthesis (United States)

    Casey, Charles P.


    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…

  16. 1-Isocyano-2-dimethylamino-alkenes: Versatile reagents in diversity-oriented organic synthesis

    NARCIS (Netherlands)

    Dömling, Alexander; Illgen, Katrin


    1-Isocyano-2-dimethylamino-alkenes are versatile and multifunctional reagents in organic synthesis. Two useful protocols are given for multicomponent reactions (MCRs) for the assembly of a 6-oxo-1,4,5,6-tetrahydropyrazine-2- carboxylic acid methyl ester derivative and a highly substituted thiazole.

  17. Interdisciplinary Learning for Chemical Engineering Students from Organic Chemistry Synthesis Lab to Reactor Design to Separation (United States)

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


    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…

  18. Synthesis and Hydrogenation of Disubstituted Chalcones: A Guided-Inquiry Organic Chemistry Project (United States)

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


    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…

  19. 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.


    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

  20. Carbon dioxide capture and use: organic synthesis using carbon dioxide from exhaust gas. (United States)

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


    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. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    CERN Document Server

    Clerici, Mario G


    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

  2. Synthesis, Postmodification, Metalation, and Gas Adsorption in Chemically Stable Metal Organic Frameworks and Zeolitic Imidazolate Frameworks.


    Morris, William


    Metal Organic Frameworks (MOFs) and Zeolitic Imidazolate Frameworks (ZIFs) are porous crystalline materials comprised of organic units (links) and metal oxide units (secondary building units) with surface areas often exceeding 1000 m2/g. These materials are finding increased applications in gas storage, gas separation, and catalysis. In this thesis new MOFs and ZIFs are synthesized to further these applications. Special attention is paid to the synthesis of frameworks, which can be postsynthe...

  3. Synthesis and characterization of a new organic semiconductor material

    Energy Technology Data Exchange (ETDEWEB)

    Tiffour, Imane [Laboratoire de Génie Physique, Département de Physique, Université de Tiaret, Tiaret 14000 (Algeria); Faculté des Sciences et Technologies, Université Mustapha Stambouli, Mascara 29000 (Algeria); Dehbi, Abdelkader [Laboratoire de Génie Physique, Département de Physique, Université de Tiaret, Tiaret 14000 (Algeria); Mourad, Abdel-Hamid I., E-mail: [Mechanical Engineering Department, Faculty of Engineering, United Arab Emirates University, Al-Ain, P.O. Box 15551 (United Arab Emirates); Belfedal, Abdelkader [Faculté des Sciences et Technologies, Université Mustapha Stambouli, Mascara 29000 (Algeria); LPCMME, Département de Physique, Université d' Oran Es-sénia, 3100 Oran (Algeria)


    The objective of this study is to create an ideal mixture of Acetaminophen/Curcumin leading to a new and improved semiconductor material, by a study of the electrical, thermal and optical properties. This new material will be compared with existing semiconductor technology to discuss its viability within the industry. The electrical properties were investigated using complex impedance spectroscopy and optical properties were studied by means of UV-Vis spectrophotometry. The electric conductivity σ, the dielectric constant ε{sub r}, the activation energy E{sub a}, the optical transmittance T and the gap energy E{sub g} have been investigated in order to characterize our organic material. The electrical conductivity of the material is approximately 10{sup −5} S/m at room temperature, increasing the temperature causes σ to increase exponentially to approximately 10{sup −4} S/m. The activation energy obtained for the material is equal to 0.49 ± 0.02 ev. The optical absorption spectra show that the investigating material has absorbance in the visible range with a maximum wavelength (λ{sub max}) 424 nm. From analysis, the absorption spectra it was found the optical band gap equal to 2.6 ± 0.02 eV and 2.46 ± 0.02 eV for the direct and indirect transition, respectively. In general, the study shows that the developed material has characteristics of organic semiconductor material that has a promising future in the field of organic electronics and their potential applications, e.g., photovoltaic cells. - Highlights: • Development of a new organic acetaminophen/Curcumin semiconductor material. • The developed material has characteristics of an organic semiconductor. • It has electrical conductivity comparable to available organic semiconductors. • It has high optical transmittance and low permittivity/dielectric constant.

  4. Synthesis, characterization and application of an inorgano organic ...

    Indian Academy of Sciences (India)

    Its chemical stability has been assessed in various mineral acids, bases and organic solvents. Ion exchange capacity (IEC) has been determined and distribution behaviour towards several metal ions in different electrolyte solutions with varying concentrations has been studied and a few binary separations achieved.

  5. Green chemistry principles in organic compound synthesis and analysis

    Directory of Open Access Journals (Sweden)

    Ruchi Verma


    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.

  6. Burnout and Organization in Education: A Synthesis of Literature. (United States)

    Gibson, R. Oliver; Raw, Donald W.

    Burnout in education is described in terms of system stress. Systems and their relationships are viewed at four levels: somatic, psychological, social, and cultural. "Burnout" is defined as a reduction of the function of an organism or living system. Changes in the state of a system create increased demands for adaptation. Stress is a general…

  7. Organic Synthesis under Solvent-free Condition. An Environmentally ...

    Indian Academy of Sciences (India)

    environmental pollution caused by solvents and also their academic interest in solid-solid reactions have led them in recent times to develop methodologies for solvent-free reac- tions with considerable success. The Function of a Solvent. A general assumption with regard to organic reactions is that they are performed in a ...

  8. Experimental Investigation of Organic Synthesis in Hydrothermal Environments (United States)

    Shock, Everett L.


    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.

  9. Organic ambipolar conjugated molecules for electronics: synthesis and structure-property relationships. (United States)

    Jiang, Hongji


    The field of organic electronics has been developed vastly in the past two decades, and the performance and lifetime of these devices are critically dependent on the materials development, device design, deposition processes, and modeling, among which the active materials of organic semiconductor play a crucial role. The unique properties of organic semiconductor are largely based on the versatility to synthesize multifunctional organic conjugated materials by judicious molecular design. To effectively adjust the optoelectronic properties, especially energy levels, of organic semiconductor, the scientists have presented a synthesis methodology of organic ambipolar conjugated molecules, in which typical p-dope type and n-dope type segments are incorporated into one molecule. The present review summarizes the progress on organic ambipolar conjugated molecules for electronics in the past few years. Some issues to be addressed are also highlighted and discussed. Copyright © 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Bupivacaine decreases cell viability and matrix protein synthesis in an intervertebral disc organ model system. (United States)

    Wang, Dong; Vo, Nam V; Sowa, Gwendolyn A; Hartman, Robert A; Ngo, Kevin; Choe, So Ra; Witt, William T; Dong, Qing; Lee, Joon Y; Niedernhofer, Laura J; Kang, James D


    Bupivacaine is a local anesthetic commonly used for back pain management in interventional procedures. Cytotoxic effects of bupivacaine have been reported in articular cartilage and, recently, in intervertebral disc cell culture. However, the relevance of these effects to discs in vivo remains unclear. This study examines the effect of bupivacaine on disc cell metabolism using an organotypic culture model system that mimics the in vivo environment. To assess the effect of bupivacaine on disc cell viability and matrix protein synthesis using an organotypic model system and to determine whether this anesthetic has toxic effects. Mouse intervertebral discs were isolated and maintained ex vivo in an organotypic culture then exposed to clinically relevant concentrations of bupivacaine, and the impact on disc cell viability and matrix proteoglycan (PG) and collagen syntheses were measured in the presence and absence of the drug. Mouse functional spine units (FSUs) were isolated from the lumbar spines of 10-week-old mice. Cell viability was assessed by 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assay. Total PG and collagen syntheses were determined by measuring the incorporation of radioactive (35)S-sulfate and (3)H-l-proline into PG and collagen, respectively. Organotypic cultures of mouse FSUs were exposed to different concentrations (0%-0.5%) of bupivacaine for variable amounts of time (0-2 hours). Cell viability within disc tissue was quantified by MTT staining and histologic assay. Matrix protein synthesis was measured by incorporation of radioactive (35)S-sulfate (for PG synthesis) and (3)H-l-proline (for collagen synthesis). Untreated mouse disc organs were maintained in culture for up to 1 month with minimal changes in tissue histology, cell viability, and matrix protein synthesis. Exposure to bupivacaine decreased cell viability in a dose- and time-dependent manner. Exposure to bupivacaine at concentrations less than or equal to 0.25% did

  11. Hyaluronate synthesis by synovial villi in organ culture. [Dogs

    Energy Technology Data Exchange (ETDEWEB)

    Myers, S.L.; Christine, T.A.


    Individual canine synovial villi were used to establish short-term synovial organ cultures. These villi incorporated /sup 3/H-glucosamine into highly-polymerized /sup 3/H-hyaluronic acid (/sup 3/H-HA), which was the only /sup 3/H-glycosaminoglycan identified in the culture medium. Some /sup 3/H-HA, and larger amounts of other /sup 3/H-glycosaminoglycans, were recovered from cultured tissues. Culture medium /sup 3/H-HA content was proportional to the surface area of cultured villi. Organ cultures of nonvillous synovium were compared with villi; nonvillous cultures synthesized less /sup 3/H-HA per mm2 of their synovial intimal surface than villi. These cultures complement cell culture techniques for in vitro studies of synovial lining cell function.

  12. Synthesis of Amino Acid Precursors with Organic Solids in Planetesimals with Liquid Water (United States)

    Kebukawa, Y; Misawa, S.; Matsukuma, J.; Chan, Q. H. S.; Kobayashi, J.; Tachibana, S.; Zolensky, M. E.


    Amino acids are important ingredients of life that would have been delivered to Earth by extraterrestrial sources, e.g., comets and meteorites. Amino acids are found in aqueously altered carbonaceous chondrites in good part in the form of precursors that release amino acids after acid hydrolysis. Meanwhile, most of the organic carbon (greater than 70 weight %) in carbonaceous chondrites exists in the form of solvent insoluble organic matter (IOM) with complex macromolecular structures. Complex macromolecular organic matter can be produced by either photolysis of interstellar ices or aqueous chemistry in planetesimals. We focused on the synthesis of amino acids during aqueous alteration, and demonstrated one-pot synthesis of a complex suite of amino acids simultaneously with IOM via hydrothermal experiments simulating the aqueous processing

  13. Synthesis of Carbon Nanotubes and Volatile Organic Compounds Detection

    Directory of Open Access Journals (Sweden)

    Sobri S.


    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.

  14. Toward an experimental synthesis of the chondritic insoluble organic matter (United States)

    Biron, Kasia; Derenne, Sylvie; Robert, FrançOis; Rouzaud, Jean-NoëL.


    Based on the statistical model proposed for the molecular structure of the insoluble organic matter (IOM) isolated from the Murchison meteorite, it was recently proposed that, in the solar T-Tauri disk regions where (photo)dissociation of gaseous molecules takes place, aromatics result from the cyclization/aromatization of short aliphatics. This hypothesis is tested in this study, with n-alkanes being submitted to high-frequency discharge at low pressure. The contamination issue was eliminated using deuterated precursor. IOM was formed and studied using solid-state nuclear magnetic resonance, pyrolysis coupled to gas chromatography and mass spectrometry, RuO4 oxidation, and high-resolution transmission electron microscopy. It exhibits numerous similarities at the molecular level with the hydrocarbon backbone of the natural IOM, reinforcing the idea that the initial precursors of the IOM were originally chains in the gas. Moreover, a fine comparison between the chemical structure of several meteorite IOM suggests either that (i) the meteorite IOMs share a common precursor standing for the synthetic IOM or that (ii) the slight differences between the meteorite IOMs reflect differences in their environment at the time of their formation i.e., related to plasma temperature that, in turn, dictates the dissociation-recombination rates of organic fragments.

  15. Structural versatility of Metal-organic frameworks: Synthesis and Characterization

    KAUST Repository

    Alsadun, Norah S.


    Metal-Organic Frameworks (MOFs), an emerging class of porous crystalline materials, have shown promising properties for diverse applications such as catalysis, gas storage and separation. The high degree of tunability of MOFs vs other solid materials enable the assembly of advanced materials with fascinating properties for specific applications. Nevertheless, the precise control in the construction of MOFs at the molecular level remains challenging. Particularly, the formation of pre-targeted multi-nuclear Molecular Building Block (MBB) precursors to unveil materials with targeted structural characteristics is captivating. The aim of my master project in the continuous quest of the group of Prof. Eddaoudi in exploring different synthetic pathways to control the assembly of Rare Earth (RE) based MOF. After giving a general overview about MOFs, I will discuss in this thesis the results of my work on the use of tri-topic oriented organic carboxylate building units with the aim to explore the assembly/construction of new porous RE based MOFs. In chapter 2 will discuss the assembly of 3-c linkers with RE metals was then evaluated based on symmetry and angularity of the three connected linkers. The focus of chapter 3 is cerium based MOFs and heterometallic system, based on 3-c ligands with different length and symmetry. Overall, the incompatibility of 3-c ligands with the 12-c cuo MBB did not allow to any formation of higher neuclearity (˃6), but it has resulted in affecting the connectivity of the cluster.

  16. Trophic magnification of organic chemicals: A global synthesis (United States)

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


    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.

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

    Directory of Open Access Journals (Sweden)

    David R Halpin


    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.

  18. Histidine as a catalyst in organic synthesis: A facile in situ synthesis ...

    Indian Academy of Sciences (India)


    (Aldrich, E-Merck and Acros) and were purified prior to use either by distillation or by recrystallization. Histidine (E-Merck) ... ethylacetate (E-Merck) were purified by distillation before use. Double distilled water, .... Sandler S R and Karo W 1972 Organic functional group preparations (New York: Academic. Press) vol. 3. 4.

  19. Perspective: Whither the problem list? Organ-based documentation and deficient synthesis by medical trainees. (United States)

    Kaplan, Daniel M


    The author argues that the well-formulated problem list is essential for both organizing and evaluating diagnostic thinking. He considers evidence of deficiencies in problem lists in the medical record. He observes a trend among medical trainees toward organizing notes in the medical record according to lists of organ systems or medical subspecialties and hypothesizes that system-based documentation may undermine the art of problem formulation and diagnostic synthesis. Citing research linking more sophisticated problem representation with diagnostic success, he suggests that documentation style and clinical reasoning are closely connected and that organ-based documentation may predispose trainees to several varieties of cognitive diagnostic error and deficient synthesis. These include framing error, premature or absent closure, failure to integrate related findings, and failure to recognize the level of diagnostic resolution attained for a given problem. He acknowledges the pitfalls of higher-order diagnostic resolution, including the application of labels unsupported by firm evidence, while maintaining that diagnostic resolution as far as evidence permits is essential to both rational care of patients and rigorous education of learners. He proposes further research, including comparison of diagnostic efficiency between organ- and problem-oriented thinkers. He hypothesizes that the subspecialty-based structure of academic medical services helps perpetuate organ-system-based thinking, and calls on clinical educators to renew their emphasis on the formulation and documentation of complete and precise problem lists and progressively refined diagnoses by trainees.

  20. Nano-Biohybrids: In Vivo Synthesis of Metal-Organic Frameworks inside Living Plants. (United States)

    Richardson, Joseph J; Liang, Kang


    Plants have a complex passive fluid transport system capable of internalizing small molecules from the environment, and this system offers an ideal route for augmenting plants with functional nanomaterials. Current plant augmentation techniques use pre-formed nanomaterials and permeabilizing agents or plant cuttings. A so far unexplored concept is the formation of the functional material, in situ, from precursors small enough to be passively internalized through the roots without harming the plants. Metal-organic frameworks are ideal for in situ synthesis as they are composed of metal ions coordinated with organic ligands and have recently been mineralized around single-celled organisms in mild aqueous conditions. Herein, the synthesis of two types of metal-organic frameworks, zinc(2-methylimidazole) 2 and lanthanide 2 (terephthalate) 3 , are reported inside a variety of plants. In situ synchrotron experiments help elucidate the formation kinetics and crystal phases of the nano-biohybrid plants. Plants augmented with luminescent metal-organic frameworks are utilized for small molecule sensing, although other applications, such as pathogen sensing, proton conductive plants, improved CO 2 capture, bacteria-free nitrogen fixation, drought and fungi-resistance, and enhanced photosynthesis and photocatalysis, are foreseeable. Overall, the generation of functional materials inside of fully intact plants could lead to more complex nano-biohybrid sensors and organisms augmented with superior performance characteristics. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Aerosol-assisted synthesis of hierarchically organized titania and titanates nanostructures


    DUGANDŽIĆ, Ivan; Jovanović, Dragana; Mančić, Lidija; Šaponjić, Zoran; Nedeljković, Jovan; Milošević, Olivera


    The aerosol route, representing a feasible bottom-up technique for nanomaterials processing in disperse system, was applied for the low-temperature (T=150 oC) synthesis of spherical, nonagglomerated, hierarchically organized titania and titanates nanostructures. The diverse levels of structural, morphological and functional complexity were explored by using appropriate colloidal precursors comprising either spherical nanoparticles or nanotubes. In both cases, spherical, grained, submicronic s...

  2. Metal Organic Frameworks: Explorations and Design Strategies for MOF Synthesis

    KAUST Repository

    AbdulHalim, Rasha


    Metal-Organic Frameworks (MOFs) represent an emerging new class of functional crystalline solid-state materials. In the early discovery of this now rapidly growing class of materials significant challenges were often encountered. However, MOFs today, with its vast structural modularity, reflected by the huge library of the available chemical building blocks, and exceptional controlled porosity, stand as the most promising candidate to address many of the overbearing societal challenges pertaining to energy and environmental sustainability. A variety of design strategies have been enumerated in the literature which rely on the use of predesigned building blocks paving the way towards potentially more predictable structures. The two major design strategies presented in this work are the molecular building block (MBB) and supermolecular building block (SBB) -based approaches for the rationale assembly of functional MOF materials with the desired structural features. In this context, we targeted two highly connected MOF platforms, namely rht-MOF and shp-MOF. These two MOF platforms are classified based on their topology, defined as the underlying connectivity of their respective net, as edge transitive binodal nets; shp being (4,12)-connected net and rht being (3,24)-connected net. These highly connected nets were deliberately targeted due to the limited number of possible nets for connecting their associated basic building units. Two highly porous materials were designed and successfully constructed; namely Y-shp-MOF-5 and rht-MOF-10. The Y-shp-MOF-5 features a phenomenal water stability with an exquisite behavior when exposed to water, positioning this microporous material as the best adsorbent for moisture control applications. The shp-MOF platform proved to be modular to ligand functionalization and thus imparting significant behavioral changes when hydrophilic and hydrophobic functionalized ligands were introduced on the resultant MOF. On the other hand, rht

  3. Simplified Application of Material Efficiency Green Metrics to Synthesis Plans: Pedagogical Case Studies Selected from "Organic Syntheses" (United States)

    Andraos, John


    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…

  4. Benefits of Using a Problem-Solving Scaffold for Teaching and Learning Synthesis in Undergraduate Organic Chemistry I (United States)

    Sloop, Joseph C.; Tsoi, Mai Yin; Coppock, Patrick


    A problem-solving scaffold approach to synthesis was developed and implemented in two intervention sections of Chemistry 2211K (Organic Chemistry I) at Georgia Gwinnett College (GGC). A third section of Chemistry 2211K at GGC served as the control group for the experiment. Synthesis problems for chapter quizzes and the final examination were…

  5. Solution-Phase Synthesis of Dipeptides: A Capstone Project That Employs Key Techniques in an Organic Laboratory Course (United States)

    Marchetti, Louis; DeBoef, Brenton


    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…

  6. Natural abiotic formation of furans in soil. (United States)

    Huber, Stefan G; Wunderlich, S; Schöler, Heinz F; Williams, J


    Furan and its derivates are a potentially important, and little studied, class of volatile organic compounds of relevance to atmospheric chemistry. The emission of these reactive compounds has been attributed previously to biomass burning processes and biogenic sources. This paper investigates the natural abiotic formation of furans in soils, induced by the oxidation of organic matter by iron(III) and hydrogen peroxide. Several model compounds like catechol, substituted catechols, and phenols as well as different organic-rich soil samples were investigated for the release of furans. The measurements were performed with a purge and trap GC/MS system and the influence of hydrogen peroxide, reaction temperature, iron(III), pH, and reaction time on furan yield was determined. The optimal reaction turnover obtained with catechol was 2.33 microg of furan from 0.36 mg of carbon. Results presented in this paper show that a cleavage of catechol into a C2- and a C4-fragment occurs, in which the C4-fragment forms furan by integrating an oxygen atom stemming from H2O2. Furthermore, phenols could be transformed into catecholic structures under these Fenton-like conditions and also display the formation of furans. In conclusion, catalytic amounts of iron(III), the presence of hydrogen peroxide, and acidic conditions can be seen as the most important parameters required for an optimized furan formation.

  7. Integrated process of distillation with side reactors for synthesis of organic acid esters (United States)

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


    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. Organization Development and U.S. Institutions of Higher Education: A Thematic Meta-Synthesis of Approaches and Practice (United States)

    Overstreet, Kirk E., Jr.


    Organization Development (OD) has been used in a variety of ways to improve organizations both large and small. Interestingly, the institutions that teach and conduct research on organizations have been slow to adopt or utilize OD approaches and practices in their own institutions. This dissertation will use a thematic meta-synthesis approach to…

  9. Abiotic racemization kinetics of amino acids in marine sediments

    DEFF Research Database (Denmark)

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


    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...... for aspartic acid, glutamic acid, serine, and alanine in bulk sediment from Aarhus Bay, Denmark, taken from the surface, 30 cm, and 340 cm depth. Extrapolation to a typical cold deep sea sediment temperature of 3 °C suggests racemization rate constants of on the order of 10-5 yr-1 without evident differences...... 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...

  10. Effects of abiotic stress on plants: a systems biology perspective. (United States)

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


    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 dynamic activities of that organism in different environments. In this review, research progress in plant responses to abiotic stresses is summarized from the physiological level to the molecular level. New insights obtained from the integration of omics datasets are highlighted. Gaps in our knowledge are identified, providing additional focus areas for crop improvement research in the future.

  11. Fluid-induced organic synthesis in the solar nebula recorded in extraterrestrial dust from meteorites. (United States)

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


    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.


    Directory of Open Access Journals (Sweden)

    Pirog T. P.


    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.

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

    KAUST Repository

    Alamer, Badriah


    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.

  14. Titania may produce abiotic oxygen atmospheres on habitable exoplanets


    Norio Narita; Takafumi Enomoto; Shigeyuki Masaoka; Nobuhiko Kusakabe


    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 ...

  15. Marine invertebrates, model organisms, and the modern synthesis: epistemic values, evo-devo, and exclusion. (United States)

    Love, Alan C


    A central reason that undergirds the significance of evo-devo is the claim that development was left out of the Modern synthesis. This claim turns out to be quite complicated, both in terms of whether development was genuinely excluded and how to understand the different kinds of embryological research that might have contributed. The present paper reevaluates this central claim by focusing on the practice of model organism choice. Through a survey of examples utilized in the literature of the Modern synthesis, I identify a previously overlooked feature: exclusion of research on marine invertebrates. Understanding the import of this pattern requires interpreting it in terms of two epistemic values operating in biological research: theoretical generality and explanatory completeness. In tandem, these values clarify and enhance the significance of this exclusion. The absence of marine invertebrates implied both a lack of generality in the resulting theory and a lack of completeness with respect to particular evolutionary problems, such as evolvability and the origin of novelty. These problems were salient to embryological researchers aware of the variation and diversity of larval forms in marine invertebrates. In closing, I apply this analysis to model organism choice in evo-devo and discuss its relevance for an extended evolutionary synthesis.

  16. Harnessing the Power of the Water-Gas Shift Reaction for Organic Synthesis. (United States)

    Ambrosi, Andrea; Denmark, Scott E


    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. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. 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: [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)


    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.

  18. Structure-directing effects of ionic liquids in the ionothermal synthesis of metal–organic frameworks

    Directory of Open Access Journals (Sweden)

    Thomas P. Vaid


    Full Text Available Traditional synthesis of metal–organic frameworks (MOFs involves the reaction of a metal-containing precursor with an organic linker in an organic solvent at an elevated temperature, in what is termed a `solvothermal' reaction. More recently, many examples have been reported of MOF synthesis in ionic liquids (ILs, rather than an organic solvent, in `ionothermal' reactions. The high concentration of both cations and anions in an ionic liquid allows for the formation of new MOF structures in which the IL cation or anion or both are incorporated into the MOF. Most commonly, the IL cation is included in the open cavities of the MOF, countering the anionic charge of the MOF framework itself and acting as a template around which the MOF structure forms. Ionic liquids can also serve other structure-directing roles, for example, when an IL containing a single enantiomer of a chiral anion leads to a homochiral MOF, even though the IL anion is not itself incorporated into the MOF. A comprehensive review of ionothermal syntheses of MOFs, and the structure-directing effects of the ILs, is given.

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


    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.

  20. Synthesis of a specified, silica molecular sieve by using computationally predicted organic structure-directing agents. (United States)

    Schmidt, Joel E; Deem, Michael W; Davis, Mark E


    Crystalline molecular sieves are used in numerous applications, where the properties exploited for each technology are the direct consequence of structural features. New materials are typically discovered by trial and error, and in many cases, organic structure-directing agents (OSDAs) are used to direct their formation. Here, we report the first successful synthesis of a specified molecular sieve through the use of an OSDA that was predicted from a recently developed computational method that constructs chemically synthesizable OSDAs. Pentamethylimidazolium is computationally predicted to have the largest stabilization energy in the STW framework, and is experimentally shown to strongly direct the synthesis of pure-silica STW. Other OSDAs with lower stabilization energies did not form STW. The general method demonstrated here to create STW may lead to new, simpler OSDAs for existing frameworks and provide a way to predict OSDAs for desired, theoretical frameworks. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Direct Synthesis of 7 nm Thick Zinc(II)-Benzimidazole-Acetate Metal-Organic Framework Nanosheets

    Energy Technology Data Exchange (ETDEWEB)

    Xue, Feng; Kumar, Prashant; Xu, Wenqian; Mkhoyan, K. Andre; Tsapatsis, Michael


    Two-dimensional metal-organic frameworks (MOFs) are promising candidates for high performance gas sepa-ration membranes. Currently, MOF nanosheets are mostly fabricated through delamination of layered MOFs, which often re-sults in a low yield of intact free-standing nanosheets. In this work, we present a direct synthesis method for zinc(II)-benzimidazole-acetate (Zn(Bim)OAc) MOF nanosheets. The obtained nanosheets have a lateral dimension of 600 nm when synthesized at room temperature. By adjusting the synthesis temperature, the morphology of obtained nanosheets can be readily tuned from nanosheets to nanobelts. A thickness of 7 nm is determined for Zn(Bim)OAc using high-angle annular dark-field scanning transmission electron microscopy, which makes these nanosheets promising building blocks of gas sepa-ration membranes.

  2. Recent Developments of Metal and Metal Oxide Nanocatalysts in Organic Synthesis. (United States)

    Makawana, Jigar A; Sangani, Chetan B; Yao, Yong-Fang; Duan, Yong-Tao; Lv, Peng-Cheng; Zhu, Hai-Liang


    Recently, various nanomaterials have been used in many organic transformations as efficient catalysts. The development of new catalysts by nanoscale design has emerged as a fertile field for research and innovation. The ability of nanotechnology to enhance catalytic activity opens the potential to replace expensive catalysts with lower amounts of inexpensive nanocatalysts. Besides, development of efficient and environmentally friendly synthetic methodologies for the synthesis of compound libraries of medicinal scaffolds is an attractive area of research in both academic and pharmaceutical industry. According to above reports and needs, this review deals with applications of nanoparticles as catalysts in various organic syntheses. We detail the topic of organic transformations using nanoparticles: Metal Nanoparticles and Metal Oxide Nanoparticles. In the latter part, different Metal Oxide Nanoparticles, such as ZnO Nanoparticle, TiO2 Nanoparticle, and CuO Nanoparticle are discussed.

  3. A Research Module for the Organic Chemistry Laboratory: Multistep Synthesis of a Fluorous Dye Molecule. (United States)

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


    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.

  4. Metal-organic frameworks: structure, properties, methods of synthesis and characterization (United States)

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


    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.

  5. Environmentally friendly synthesis of organic-soluble silver nanoparticles for printed electronics

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Kwi Jong; Jun, Byung Ho; Choi, Junrak; Lee, Young Il; Joung, Jaewoo; Oh, Yong Soo [eMD Center, Samsung Electro-Mechanics, Suwon, Kyunggi-Do 443-743 (Korea, Republic of)


    In this study, we attempted to synthesize organic-soluble silver nanoparticles in the concentrated organic phase with an environmentally friendly method. The fully organic phase system contains silver acetate as a silver precursor, oleic acid as both a medium and a capping molecule, and tin acetate as a reducing agent. Monodisperse silver nanoparticles with average diameters of ca. 5 nm can be easily synthesized at large scale. Only a small usage of tin acetate (<0.05 eq.mol) resulted in a high synthesis yield (>90%). Also, it was investigated that the residual tin atom does not exist in the synthesized silver nanoparticles. This implied that tin acetate acts as a reducing catalyst.

  6. Abiotic controls on N2O emissions from soils and wetlands (United States)

    Horwath, W. R.


    The increase in atmospheric nitrous oxide (N2O) is a critical climate change issue contributing to global warming. Most studies on N2O production attribute microbial processes and their associated enzymatic reactions to be the main driver affecting emissions. The role of redox capable iron, manganese and organic compounds that can react with intermediates in the nitrogen cycle has also been shown to produce N2O abiotically. The importance of the abiotic pathways, however, is highly debated. The abiotic production of N2O is related to biophysiochemical controls and unique isotopic signatures of nitrogen cycle intermediates (hydroxylamine, nitric oxide, and nitrite), redox-active metals (iron and manganese) and organic matter (humic and fulvic acids). In a range of soils, we find that the iron directly associated with organic compounds is the strongest variable relating to N2O emissions. In addition to these factors, management is also assumed to affect abiotic N2O production through its impact on nitrogen cycle intermediates, but the environmental and physiochemical conditions that are changed by management are rarely considered in the abiotic production of N2O. We find that the amount and quality of organic compounds in soils directly determines the fate of soil N2O production (i.e. be emitted or consumed). Water depth in rice paddies and wetlands also plays a significant role in partitioning production and consumption of N2O. What is evident from studies on N2O emission is that abiotic reactions are coupled to biotic processes and they cannot be easily separated. The biotic/abiotic interactions have important ecological outcomes that influence abiotic production mechanisms and should be recognized as important controllers of N2O production and consumption processes in soils and sediments.

  7. Advances in Electrocatalysis for Energy Conversion and Synthesis of Organic Molecules. (United States)

    Holade, Yaovi; Servat, Karine; Tingry, Sophie; Napporn, Teko W; Remita, Hynd; Cornu, David; Kokoh, K Boniface


    Ubiquitous electrochemistry is expected to play a major role for reliable energy supply as well as for production of sustainable fuels and chemicals. The fundamental understanding of organics-based electrocatalysis in alkaline media at the solid-liquid interface involves complex mechanisms and performance descriptors (from the electrolyte and reaction intermediates), which undermine the roads towards advance and breakthroughs. Here, we review and diagnose recently designed strategies for the electrochemical conversion of organics into electricity and/or higher-value chemicals. To tune the mysterious workings of nanocatalysts in electrochemical devices, we examine the guiding principles by which the performance of a particular electrode material is governed, thus highlighting various tactics for the development of synthesis methods for nanomaterials with specific properties. We end by examining the production of chemicals by using electrochemical methods, from selective oxidation to reduction reactions. The intricate relationship between electrode and selectivity encourages both of the communities of electrocatalysis and organic synthesis to move forward together toward the renaissance of electrosynthesis methods. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Synthesis of Zeolites Using the ADOR (Assembly-Disassembly-Organization-Reassembly) Route. (United States)

    Wheatley, Paul S; Čejka, Jiří; Morris, Russell E


    Zeolites are an important class of materials that have wide ranging applications such as heterogeneous catalysts and adsorbents which are dependent on their framework topology. For new applications or improvements to existing ones, new zeolites with novel pore systems are desirable. We demonstrate a method for the synthesis of novel zeolites using the ADOR route. ADOR is an acronym for Assembly, Disassembly, Organization and Reassembly. This synthetic route takes advantage of the assembly of a relatively poorly stable that which can be selectively disassembled into a layered material. The resulting layered intermediate can then be organized in different manners by careful chemical manipulation and then reassembled into zeolites with new topologies. By carefully controlling the organization step of the synthetic pathway, new zeolites with never before seen topologies are capable of being synthesized. The structures of these new zeolites are confirmed using powder X-ray diffraction and further characterized by nitrogen adsorption and scanning electron microscopy. This new synthetic pathway for zeolites demonstrates its capability to produce novel frameworks that have never been prepared by traditional zeolite synthesis techniques.

  9. Genes Acting on Transcriptional Control during Abiotic Stress Responses

    Directory of Open Access Journals (Sweden)

    Glacy Jaqueline da Silva


    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.

  10. Applications of Continuous-Flow Photochemistry in Organic Synthesis, Material Science, and Water Treatment. (United States)

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


    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.

  11. Nobel Prize in Chemistry. Development of the Olefin Metathesis Method in Organic Synthesis (United States)

    Casey, Charles P.


    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 .

  12. Metal-organic framework templated synthesis of porous inorganic materials as novel sorbents

    Energy Technology Data Exchange (ETDEWEB)

    Taylor-Pashow, Kathryn M. L.; Lin, Wenbin; Abney, Carter W.


    A novel metal-organic framework (MOF) templated process for the synthesis of highly porous inorganic sorbents for removing radionuclides, actinides, and heavy metals is disclosed. The highly porous nature of the MOFs leads to highly porous inorganic sorbents (such as oxides, phosphates, sulfides, etc) with accessible surface binding sites that are suitable for removing radionuclides from high level nuclear wastes, extracting uranium from acid mine drainage and seawater, and sequestering heavy metals from waste streams. In some cases, MOFs can be directly used for removing these metal ions as MOFs are converted to highly porous inorganic sorbents in situ.

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

    KAUST Repository

    Eddaoudi, Mohamed


    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.

  14. Zeolite-like metal-organic frameworks (ZMOFs): design, synthesis, and properties. (United States)

    Eddaoudi, Mohamed; Sava, Dorina F; Eubank, Jarrod F; Adil, Karim; Guillerm, Vincent


    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.

  15. Synthesis and characterization of organic-inorganic hybrids formed between conducting polymers and crystalline antimonic acid

    Directory of Open Access Journals (Sweden)

    Beleze Fábio A.


    Full Text Available In this paper we report the synthesis and characterization of novel organic-inorganic hybrid materials between the crystalline antimonic acid (CAA and two conductive polymers: polypyrrole and polyaniline. The hybrids were obtained by in situ oxidative polymerization of monomers by the Sb(V present in the pyrochlore-like CAA structure. The materials were characterized by infrared and Raman spectroscopy, X-ray diffraction, cyclic voltammetry, CHN elemental analysis and electronic paramagnetic resonance spectroscopy. The results showed that both polymers were formed in their oxidized form, with the CAA structure acting as a counter anion.

  16. Interface modification and material synthesis of organic light-emitting diodes using plasma technology (United States)

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


    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.

  17. An unconventional rapid synthesis of high performance metal-organic framework membranes. (United States)

    Shah, Miral N; Gonzalez, Mariel A; McCarthy, Michael C; Jeong, Hae-Kwon


    Metal-organic frameworks (MOFs) are attractive for gas separation membrane applications due to their microporous channels with tunable pore shape, size, and functionality. Conventional MOF membrane fabrication techniques, namely in situ and secondary growth, pose challenges for their wider commercial applications. These challenges include reproducility, scalability, and high manufacturing cost. Recognizing that the coordination chemistry of MOFs is fundamentally different from the covalent chemistry of zeolites, we developed a radically different strategy for MOF membrane synthesis. Using this new technique, we were able to produce continuous well-intergrown membranes of prototypical MOFs, HKUST-1 and ZIF-8, in a relatively short period of time (tens of min). With a minimal consumption of precursors and a greatly simplified synthesis protocol, our new technique provides potential for a continuous, scalable, reproducible, and easily commercializable route for the rapid synthesis of MOF membranes. RTD-prepared MOF membranes show greatly improved gas separation performances as compared to those prepared by conventional solvothermal methods, indicating improved membrane microstructure.

  18. Changes in biotic and abiotic processes following mangrove clearing (United States)

    Granek, Elise; Ruttenberg, Benjamin I.


    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

  19. Saccharin Derivative Synthesis via [1,3] Thermal Sigmatropic Rearrangement: A Multistep Organic Chemistry Experiment for Undergraduate Students (United States)

    Fonseca, Custódia S. C.


    Saccharin (1,2-benzisothiazole-3-one 1,1-dioxide) is an artificial sweetener used in the food industry. It is a cheap and easily available organic compound that may be used in organic chemistry laboratory classes for the synthesis of related heterocyclic compounds and as a derivatizing agent. In this work, saccharin is used as a starting material…

  20. The transition from abiotic to biotic chemistry: When and where? (United States)

    Bada, J. L.


    /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.

  1. Integration of Fermentation and Organic Synthesis: Studies of Roquefortine C and Biosynthetic Derivatives (United States)

    Gober, Claire Marie

    Roquefortine C is one of the most ubiquitous indoline alkaloids of fungal origin. It has been isolated from over 30 different species of Penicillium fungi and has garnered attention in recent years for its role as a biosynthetic precursor to the triazaspirocyclic natural products glandicoline B, meleagrin, and oxaline. The triazaspirocyclic motif, which encompasses three nitrogen atoms attached to one quaternary carbon forming a spirocyclic scaffold, is a unique chemical moiety that has been shown to impart a wide array of biological activity, from anti-bacterial activity and antiproliferative activity against cancer cell lines to anti-biofouling against marine organisms. Despite the promise of these compounds in the pharmaceutical and materials industries, few syntheses of triazaspirocycles exist in the literature. The biosynthesis of roquefortine C-derived triazaspirocycles, however, provides inspiration for the synthesis of these compounds, namely through a nitrone-promoted transannular rearrangement. This type of internal rearrangement has never been carried out synthetically and would provide an efficient stereoselective synthesis of triazaspirocycles. This work encompasses efforts towards elucidating the biosynthetic pathway of roquefortine C-derived triazaspirocycles as well as synthetic efforts towards the construction of triazaspirocycles. Chapter 1 will discuss a large-scale fermentation procedure for the production of roquefortine C from Penicillium crustosum. Chapters 2 and 3 explore (through enzymatic and synthetic means, respectively) the formation of the key indoline nitrone moiety required for the proposed transannular rearrangement. Finally, chapter 4 will discuss synthetic efforts towards the synthesis of triazaspirocycles. This work has considerably enhanced our understanding of the roquefortine C biosynthetic pathway and the unique chemistry of this natural product, and our efforts towards the synthesis of triazaspirocycles will facilitate the

  2. Molecular mechanisms in plant abiotic stress response


    Poltronieri Palmiro; Bonsegna Stefania; De Domenico Stefania; Santino Angelo


    Improved crop varieties are needed to sustain the food supply, to fight climate changes, water scarcity, temperature increase and a high variability of rainfalls. Variability of drought and increase in soil salinity have negative effects on plant growth and abiotic stresses seriously threaten sustainable agricultural production. To overcome the influence of abiotic stresses, new tolerant plant varieties and breeding techniques using assisted selection are sought. A deep understanding of the m...

  3. Synthesis of Inorganic-Organic Hybrid Materials Designed for Radiation Detection, Luminescence, and Gas Storage (United States)

    Vaughn, Shae Anne

    Materials discovery is the driving force behind the research presented herein. Basic research has been conducted in order to obtain a better understanding of coordination chemistry and structural outcomes, particularly within the area of trivalent lanthanides. Discovering new materials is one route to further advancement of technology; another one is the focus on incremental changes to already existing materials. Often the building blocks of a compound are chosen in an effort to synthesize a material that makes use of the properties of each individual component and may result in a better, more robust, applicable material. The combination of organic and inorganic components for the synthesis of novel materials with potential applications such as scintillation photoluminescence, catalysis, and gas storage are the focus of the research presented herein. The first part focuses on lanthanide organic hybrid materials, where the synthesis of a new family of potential scintillating materials was undertaken and yielded improved understanding of the control that can be achieved over the topological structure of these materials by controlling the coordinating crystallization solvents. This research has led to the synthesis of an array of unique motifs, ranging from dimeric complexes, tetrameric complexes, to 1-D chains, and most intriguing of all, catenated tetradecanuclear rings. These rings represent the largest lanthanide rings synthesized to date, the next largest multinuclear rings, until now, were dodecanuclear complexes of alkoxides. From a basic research standpoint this is an exciting new development in lanthanide coordination chemistry and illustrates the importance of steric effects upon a system. These complexes are potential scintillators, supported by their luminescence and measurements of similar compounds that demonstrate surprising scintillation efficiencies. In the second part, other hybrid materials that have also been prepared are discussed, including the

  4. Thiophene fused azacoronenes: regioselective synthesis, self organization, charge transport, and its incorporation in conjugated polymers (United States)

    Liu, Yi; He, Bo


    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.

  5. Nanoscale luminescent lanthanide-based metal-organic frameworks: properties, synthesis, and applications (United States)

    Hu, Dongqin; Song, Yonghai; Wang, Li


    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.

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

    Energy Technology Data Exchange (ETDEWEB)

    Hu, Dongqin; Song, Yonghai; Wang, Li, E-mail: [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)


    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.

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

    Directory of Open Access Journals (Sweden)

    Manoj B. Gawande


    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.

  8. Facile synthesis of -C[double bond, length as m-dash]N- linked covalent organic frameworks under ambient conditions. (United States)

    Ding, San-Yuan; Cui, Xiao-Hui; Feng, Jie; Lu, Gongxuan; Wang, Wei


    We reported herein a facile approach for the synthesis of -C[double bond, length as m-dash]N- linked covalent organic frameworks under ambient conditions. Three known (COF-42, COF-43, and COF-LZU1) and one new (Pr-COF-42) COF materials were successfully synthesized using this method. Furthermore, this simple synthetic approach makes the large-scale synthesis of -C[double bond, length as m-dash]N- linked COFs feasible.

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

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


    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.

  10. The remarkable effect of organic salts on 1,3,5-trioxane synthesis

    Directory of Open Access Journals (Sweden)

    Liu-Yi Yin


    Full Text Available Abstract The effects of organic salts on 1,3,5-trioxane synthesis were investigated through batch reaction and continuous production experiments. The organic salts used include sodium methanesulfonate (CH3NaO3S, sodium benzenesulfonate (C6H5NaO3S, sodium 4-methylbenzenesulfonate (C7H7NaO3S, and sodium 3-nitrobenzene sulfonate (C6H4NNaO5S. It was shown that the effects of organic salts on the yield of 1,3,5-trioxane in reaction solution and distillate follow the order CH3NaO3S < C6H5NaO3S < C7H7NaO3S < C6H4NNaO5S, which is inversely related to the charge density of the anions of the organic salts. In comparison with Cl−-based salts such as magnesium chloride, organic salts have the advantages of less formic acid generation and low corrosion. Studies on water activity revealed that the effect of organic salts on the activity of water was quite small at low concentration of organic salts. UV–visible spectroscopy and vapor–liquid equilibrium experiments were performed to uncover the mechanisms that govern such effects. The results showed that the effect of organic salts on the yield of 1,3,5-trioxane relies primarily on their ability to increase the catalytic activity of sulfuric acid and increase the relative volatilities of 1,3,5-trioxane and water and of 1,3,5-trioxane and oligomers.

  11. Supramolecular self-assembled molecules as organic directing agent for synthesis of zeolites. (United States)

    Corma, Avelino; Rey, Fernando; Rius, Jordi; Sabater, Maria J; Valencia, Susana


    Solid materials with uniform micropores, such as zeolites, can act as selective catalysts and adsorbents for molecular mixtures by separating those molecules small enough to enter their pores while leaving the larger molecules behind. Zeolite A is a microporous material with a high void volume. Despite its widespread industrial use in, for example, molecular separations and in detergency, its capability as a petroleum-refining material is limited owing to its poor acid-catalytic activity and hydrothermal stability, and its low hydrophobicity. These characteristics are ultimately a consequence of the low framework Si/Al ratio (normally around one) and the resulting high cationic fraction within the pores and cavities. Researchers have modified the properties of type-A zeolites by increasing the Si/Al compositions up to a ratio of three. Here we describe the synthesis of zeolite A structures exhibiting high Si/Al ratios up to infinity (pure silica). We synthesize these materials, named ITQ-29, using a supramolecular organic structure-directing agent obtained by the self-assembly, through pi-pi type interactions, of two identical organic cationic moieties. The highly hydrophobic pure-silica zeolite A can be used for hydrocarbon separations that avoid oligomerization reactions, whereas materials with high Si/Al ratios give excellent shape-selective cracking additives for increasing propylene yield in fluid catalytic cracking operations. We have also extended the use of our supramolecular structure-directing agents to the synthesis of a range of other zeolites.

  12. Visible-Light Photocatalysis: Does it make a difference in Organic Synthesis? (United States)

    Marzo, Leyre; Pagire, Santhosh K; Reiser, Oliver; König, Burkhard


    Visible light photocatalysis has evolved over the last decade into a widely used method in organic synthesis. For many important transformations, such as cross-coupling reactions, alpha-amino functionalizations, cycloadditions, ATRA reactions, or fluorinations, photocatalytic variants have been reported. In this review, we try to compare classical and photocatalytic procedures for selected classes of reactions and highlight their advantages and limitations. In many cases, the photocatalytic reactions proceed at milder reaction conditions, typically at room temperature, and stoichiometric reagents are replaced by simple oxidants or reductants, like air oxygen or amines. This way, besides providing alternative protocols for established transformations that allow a broadening of the substrate scope, also new transformations become possible, especially by merging photocatalysis with organo- or metal catalysis. Does visible light photocatalysis make a difference in organic synthesis? The prospect to shuttle electrons back and forth to substrates and intermediates or to selectively transfer energy through a visible light absorbing photocatalyst holds the promise to improve current protocols in radical chemistry and to open up new avenues by accessing reactive species hitherto unknown. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Synthesis of a Water-soluble Metal-Organic Complex Array. (United States)

    Bose, Purnandhu; Sukul, Pradip K; Yaghi, Omar M; Tashiro, Kentaro


    We demonstrate a method for the synthesis of a water-soluble multimetallic peptidic array containing a predetermined sequence of metal centers such as Ru(II), Pt(II), and Rh(III). The compound, named as a water-soluble metal-organic complex array (WSMOCA), is obtained through 1) the conventional solution-chemistry-based preparation of the corresponding metal complex monomers having a 9-fluorenylmethyloxycarbonyl (Fmoc)-protected amino acid moiety and 2) their sequential coupling together with other water-soluble organic building units on the surface-functionalized polymeric resin by following the procedures originally developed for the solid-phase synthesis of polypeptides, with proper modifications. Traces of reactions determined by mass spectrometric analysis at the representative coupling steps in stage 2 confirm the selective construction of a predetermined sequence of metal centers along with the peptide backbone. The WSMOCA cleaved from the resin at the end of stage 2 has a certain level of solubility in aqueous media dependent on the pH value and/or salt content, which is useful for the purification of the compound.

  14. Expeditious organic-free assembly: morphologically controlled synthesis of iron oxides using microwaves (United States)

    Kou, Jiahui; Varma, Rajender S.


    A microwave hydrothermal method is developed for the synthesis of iron oxides, α-Fe2O3, β-FeOOH, and the junction of α-Fe2O3-β-FeOOH. This method is absolutely organic-free, and various structures could be obtained simply by changing the use of the iron source and NaOH. The as-prepared sea urchin-like β-FeOOH exhibits excellent catalytic performance for the degradation of methylene blue (MB) in the presence of H2O2.A microwave hydrothermal method is developed for the synthesis of iron oxides, α-Fe2O3, β-FeOOH, and the junction of α-Fe2O3-β-FeOOH. This method is absolutely organic-free, and various structures could be obtained simply by changing the use of the iron source and NaOH. The as-prepared sea urchin-like β-FeOOH exhibits excellent catalytic performance for the degradation of methylene blue (MB) in the presence of H2O2. Electronic supplementary information (ESI) available: XRD patterns and the reaction profile of the microwave system. See DOI: 10.1039/c3nr02663a

  15. Titania may produce abiotic oxygen atmospheres on habitable exoplanets. (United States)

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


    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.

  16. Synthesis of novel inorganic-organic hybrid materials for simultaneous adsorption of metal ions and organic molecules in aqueous solution

    Energy Technology Data Exchange (ETDEWEB)

    Jin, Xinliang [State Key Laboratory of Applied Organic Chemistry, College of Chemistry and Chemical Engineering, Institute of Biochemical Engineering and Environmental Technology, Lanzhou University, Lanzhou 730000 (China); Li, Yanfeng, E-mail: [State Key Laboratory of Applied Organic Chemistry, College of Chemistry and Chemical Engineering, Institute of Biochemical Engineering and Environmental Technology, Lanzhou University, Lanzhou 730000 (China); Yu, Cui; Ma, Yingxia; Yang, Liuqing; Hu, Huaiyuan [State Key Laboratory of Applied Organic Chemistry, College of Chemistry and Chemical Engineering, Institute of Biochemical Engineering and Environmental Technology, Lanzhou University, Lanzhou 730000 (China)


    Highlights: Black-Right-Pointing-Pointer Novel hybrid materials were synthesized and employed in the absorption of heavy metal and organic pollutants. Black-Right-Pointing-Pointer A novel method for amphiphilic adsorbent material synthesis was first reported in this paper. Black-Right-Pointing-Pointer The adsorbent material showed excellent adsorption capacity to Pb(II) and phenol. - Abstract: In this paper, atom transfer radical polymerization (ATRP) and radical grafting polymerization were combined to synthesize a novel amphiphilic hybrid material, meanwhile, the amphiphilic hybrid material was employed in the absorption of heavy metal and organic pollutants. After the formation of attapulgite (ATP) ATRP initiator, ATRP block copolymers of styrene (St) and divinylbenzene (DVB) were grafted from it as ATP-P(S-b-DVB). Then radical polymerization of acrylonitrile (AN) was carried out with pendent double bonds in the DVD units successfully, finally we got the inorganic-organic hybrid materials ATP-P(S-b-DVB-g-AN). A novel amphiphilic hybrid material ATP-P(S-b-DVB-g-AO) (ASDO) was obtained after transforming acrylonitrile (AN) units into acrylamide oxime (AO) as hydrophilic segment. The adsorption capacity of ASDO for Pb(II) could achieve 131.6 mg/g, and the maximum removal capacity of ASDO towards phenol was found to be 18.18 mg/g in the case of monolayer adsorption at 30 Degree-Sign C. The optimum pH was 5 for both lead and phenol adsorption. The adsorption kinetic suited pseudo-second-order equation and the equilibrium fitted the Freundlich model very well under optimal conditions. At the same time FT-IR, TEM and TGA were also used to study its structure and property.

  17. 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


    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...

  18. Progammed synthesis of magnetic mesoporous silica coated carbon nanotubes for organic pollutant adsorption

    Energy Technology Data Exchange (ETDEWEB)

    Tong, Yue; Zhang, Min, E-mail:; Xia, Peixiong; Wang, Linlin; Zheng, Jing; Li, Weizhen; Xu, Jingli, E-mail:


    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, N{sub 2} adsorption–desorption and VSM. The well-designed mesoporous magnetic nanotubes had a large specific area, a highly open mesoporous structure and high magnetization. Firstly, SiO{sub 2}-coated maghemite/CNTs nanoparticles (CNTs/Fe{sub 3}O{sub 4}@SiO{sub 2} 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 SiO{sub 2}, respectively. The CNTs/Fe{sub 3}O{sub 4}@SiO{sub 2} composites revealed a core–shell structure, Then, CNTs/Fe{sub 3}O{sub 4}@mSiO{sub 2} 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. - Graphical abstract: Magnetic mesoporous silica coated carbon nanotubes were produced from hydrophilic monodisperse magnetic nanoparticles decorated carbon nanotubes using well controlled programmed synthesis, which can be a good adsorbent for the organic pollutant in the ambient temperature. - Highlights: • The surface of CNTs/Fe{sub 3}O{sub 4} is hydrophilic, which facilitates the silica coating. • The CNTs/Fe{sub 3}O{sub 4}@mSiO{sub 2} was synthesized by a facile method. • The CNTs/Fe{sub 3}O{sub 4}@mSiO{sub 2} can be a good adsorbent for the organic pollutant.

  19. A working hypothesis for broadening framework types of zeolites in seed-assisted synthesis without organic structure-directing agent. (United States)

    Itabashi, Keiji; Kamimura, Yoshihiro; Iyoki, Kenta; Shimojima, Atsushi; Okubo, Tatsuya


    Recent research has demonstrated a new synthesis route to useful zeolites such as beta, RUB-13, and ZSM-12 via seed-assisted, organic structure-directing agent (OSDA)-free synthesis, although it had been believed that these zeolites could be essentially synthesized with OSDAs. These zeolites are obtained by adding seeds to the gels that otherwise yield other zeolites; however, the underlying crystallization mechanism has not been fully understood yet. Without any strategy, it is unavoidable to employ a trial-and-error procedure for broadening zeolite types by using this synthesis method. In this study, the effect of zeolite seeds with different framework structures is investigated to understand the crystallization mechanism of zeolites obtained by the seed-assisted, OSDA-free synthesis method. It has been found that the key factor in the successful synthesis of zeolites in the absence of OSDA is the common composite building unit contained both in the seeds and in the zeolite obtained from the gel after heating without seeds. A new working hypothesis for broadening zeolite types by the seed-assisted synthesis without OSDA is proposed on the basis of the findings of the common composite building units in zeolites. This hypothesis enables us to design the synthesis condition of target zeolites. The validity of the hypothesis is experimentally tested and verified by synthesizing several zeolites including ECR-18 in K-aluminosilicate system.

  20. Synthesis of Organic Matter of Prebiotic Chemistry at the Protoplanetary Disc (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

  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


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

  3. Enzymatic synthesis of a CCK-8 tripeptide fragment in organic media. (United States)

    Capellas, M; Benaiges, M D; Caminal, G; Gonzalez, G; Lopez-Santín, J; Clapés, P


    The enzymatic synthesis of the tripeptide derivative Z-Gly-Trp-Met-OEt is reported. This tripeptide is a fragment of the cholecystokinin C-terminal octapeptide CCK-8. Studies on the alpha-chymotrypsin catalyzed coupling reaction between Z-Gly-Trp-R(1) and Met-R(2) have focused on low water content media, using deposited enzyme on inert supports such as Celite and polyamide. The effect of additives (polar organic solvents), the acyl-donor ester structure, the C-alpha protecting group of the nucleophile, enzyme loading, and substrate concentration were tested. The best reaction medium found was acetonitrile containing buffer (0.5%, v/v) and triethylamine (0.5%, v/v) using the enzyme deposited on Celite as catalyst (8 mg of alpha-chymotrypsin/g of Celite). A reaction yield of 81% was obtained with Z-Gly-Trp-OCam as acyl donor, at an initial concentration of 80 mM. The tripeptide synthesis was scaled up to the production of 2 g of pure tripeptide with an overall yield of 71%, including reaction and purification steps.

  4. Zirconocene and Si-tethered diynes: a happy match directed toward organometallic chemistry and organic synthesis. (United States)

    Zhang, Wen-Xiong; Zhang, Shaoguang; Xi, Zhenfeng


    Characterizing reactive organometallic intermediates is critical for understanding the mechanistic aspects of metal-mediated organic reactions. Moreover, the isolation of reactive organometallic intermediates can often result in the ability to design new synthetic methods. In this Account, we outline synthetic methods that we developed for a variety of diverse Zr/Si organo-bimetallic compounds and Si/N heteroatom-organic compounds through the detailed study of zirconacyclobutene-silacyclobutene fused compounds. Two basic components are involved in this chemistry. The first is the Si-tethered diyne, which owes its rich reactive palette to the combination of the Si-C bond and the C≡C triple bond. The second is the low-valent zirconocene species Cp(2)Zr(II), which has proven very useful in organic synthesis. The reaction of these two components affords the zirconacyclobutene-silacyclobutene fused compound, which is the key reactive Zr/Si organo-bimetallic intermediate discussed here. We discuss the three types of reactions that have been developed for the zirconacyclobutene-silacyclobutene fused intermediate. The reaction with nitriles (the C≡N triple bond) is introduced in the first section. In this one-pot reaction, up to four different components can be combined: the Si-tethered diyne can be reacted with three identical nitriles, with differing nitriles, or with a nitrile and other unsaturated organic substrates such as formamides, isocyanides, acid chlorides, aldehydes, carbodiimides, and azides. Several unexpected multiring, fused Zr/Si organo-bimetallic intermediates were isolated and characterized. A wide variety of N-heterocycles, such as 5-azaindole, pyrrole, and pyrroloazepine derivatives, were obtained. We then discuss the reaction with alkynes (the C≡C triple bond). A consecutive skeletal rearrangement, differing from that observed in the reactions with nitriles, takes place in this reaction. Finally, we discuss the reaction with the C═X substrates

  5. An Efficient Synthesis Strategy for Metal-Organic Frameworks: Dry-Gel Synthesis of MOF-74 Framework with High Yield and Improved Performance. (United States)

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


    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.

  6. Organic phase synthesis of noble metal-zinc chalcogenide core-shell nanostructures. (United States)

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


    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. Copyright © 2016 Elsevier Inc. All rights reserved.

  7. A homochiral metal-organic framework as an effective asymmetric catalyst for cyanohydrin synthesis. (United States)

    Mo, Ke; Yang, Yuhua; Cui, Yong


    A homochiral metal-organic framework (MOF) of an enantiopure 2,2'-dihydroxy-1,1'-biphenyl ligand was constructed. After exchanging one proton of the dihydroxyl group for Li(I) ions, the framework is shown to be a highly efficient and recyclable heterogeneous catalyst for asymmetric cyanation of aldehydes with up to >99% ee. Compared with the homogeneous counterpart, the MOF catalyst exhibits significantly enhanced catalytic activity and enantioselectivity, especially at a low catalyst/substrate ratio, due to that the rigid framework could stabilize the catalytically active monolithium salt of biphenol against its free transformation to catalytically inactive and/or less active assemblies in reactions. The synthetic utility of the cyanation was demonstrated in the synthesis of (S)-bufuralol (a nonselective β-adrenoceptor blocking agent) with 98% ee.

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

    Directory of Open Access Journals (Sweden)

    Cheng-an TAO


    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:

  9. Anodized Aluminum Oxide Templated Synthesis of Metal-Organic Frameworks Used as Membrane Reactors. (United States)

    Yu, Yifu; Wu, Xue-Jun; Zhao, Meiting; Ma, Qinglang; Chen, Junze; Chen, Bo; Sindoro, Melinda; Yang, Jian; Han, Shikui; Lu, Qipeng; Zhang, Hua


    The incorporation of metal-organic frameworks (MOFs) into membrane-shaped architectures is of great importance for practical applications. The currently synthesized MOF-based membranes show many disadvantages, such as poor compatibility, low dispersity, and instability, which severely limit their utility. Herein, we present a general, facile, and robust approach for the synthesis of MOF-based composite membranes through the in situ growth of MOF plates in the channels of anodized aluminum oxide (AAO) membranes. After being used as catalysis reactors, they exhibit high catalytic performance and stability in the Knoevenagel condensation reaction. The high catalytic performance might be attributed to the intrinsic structure of MOF-based composite membranes, which can remove the products from the reaction zone quickly, and prevent the aggregation and loss of catalysts during reaction and recycling process. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. 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: [Dipartimento di Fisica, Universitá degli Studi di Cagliari, S.P. Monserrato-Sestu Km 0,700, 09042 Monserrato (Canada) (Italy)


    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.

  11. [Exploitation of the chemistry of magnesium carbenoids and their use in organic synthesis]. (United States)

    Satoh, Tsuyoshi


    Synthetic organic chemistry is a base of medicinal chemistry and the exploitation of new methods for carbon-carbon bond formation is of most importance in synthetic organic chemistry. Carbenes and carbenoids have long been known to be highly reactive carbon species that show a variety of unique reactivity. However, those reactive species are not fully used in organic synthesis. The reasons are as follows: one is the precursors for the generation of carbenes and carbenoids are quite limited and the other is that the reactivity of the species is too high to control. In order to solve the problem mentioned above, we used alpha-haloalkyl (or alkenyl) aryl sulfoxides as the precursors and used sulfoxide-magnesium exchange reaction for generation of much mild magnesium carbenoids. alpha-Haloalkyl (or alkenyl) aryl sulfoxides are quite easily synthesized in high overall yields. Magnesium carbenoids, cyclopropylmagnesium carbenoids, cyclobutylmagnesium carbenoids, magnesium beta-oxido carbenoids, and magnesium alkylidene carbenoids are generated at low temperature from the corresponding sulfoxides with a Grignard reagent in quantitative yields. They were found to be stable usually at below -60 degrees C for at least 30 min. The each magnesium carbenoids have their own unique reactivities and we could find many unprecedented reactions from these reactive species. Recent results for the developments of new synthetic methods based on the chemistry of magnesium carbenoids are described.

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

    KAUST Repository

    Ashri, Lubna Y.


    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

  13. Abiotic stressors and stress responses

    DEFF Research Database (Denmark)

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


    review how organisms respond and adapt to chemical- and temperature-induced stresses from molecular to population level. Using field-realistic studies, our integrative analysis aims to compare i) how molecular and physiological mechanisms related to protection, repair and energy allocation can impact...

  14. Organic reaction systems: using microcapsules and microreactors to perform chemical synthesis. (United States)

    Longstreet, Ashley R; McQuade, D Tyler


    The appetite for complex organic molecules continues to increase worldwide, especially in rapidly developing countries such as China, India, and Brazil. At the same time, the cost of raw materials and solvent waste disposal is also growing, making sustainability an increasingly important factor in the production of synthetic life-saving/improving compounds. With these forces in mind, our group is driven by the principle that how we synthesize a molecule is as important as which molecule we choose to synthesize. We aim to define alternative strategies that will enable more efficient synthesis of complex molecules. Drawing our inspiration from nature, we attempt to mimic (1) the multicatalytic metabolic systems within cells using collections of nonenzyme catalysts in batch reactors and (2) the serial synthetic machinery of fatty acid/polyketide biosynthesis using microreactor systems. Whether we combine catalysts in batch to prepare an active pharmaceutical ingredient (API) or use microreactors to synthesize small or polymeric molecules, we strive to understand the mechanism of each reaction while also developing new methods and techniques. This Account begins by examining our early efforts in the development of novel catalytic materials and characterization of catalytic systems and how these observations helped forge our current models for developing efficient synthetic routes. The Account progresses through a focused examination of design principles needed to develop multicatalyst systems using systems recently published by our group as examples. Our systems have been successfully applied to produce APIs as well as new synthetic methods. The multicatalyst section is then juxtaposed with our work in continuous flow multistep synthesis. Here, we discuss the design principles needed to create multistep continuous processes using examples from our recent efforts. Overall, this Account illustrates how multistep organic routes can be conceived and achieved using

  15. Abiotic Versus Biotic Weathering Of Olivine As Possible Biosignatures (United States)

    Longazo, Teresa G.; Wentworth, Susan J.; Clemett, Simon J.; Southam, Gordon; McKay, David S.


    ranged from tens to a few microns with textures that remained relatively sharp and were crystallographically controlled. These results were comparable to that observed in the "naturally" weathered comparison/reference grains. Chemical analysis by EDS indicates these textures correlated with the relative loss of Mg and Fe cations by diffusional processes. In contrast the biotic results indicated changes in the etching patterns on the scale of hundreds of nm, which are neither sharp nor crystallographically controlled (nanoetching). Organisms, organic debris and/or extracellular polymeric substances (biofilm) were often in close proximity or direct contact with the nanoetching. While there are many poorly constrained variables in natural weathering experiments to contend with, such as the time scale, the chemistry of the fluids and degree of biologic participation, some preliminary observations can be made: (1) certain distinct surface textures appear correlated with the specific processes giving rise to these textures; (2) the process of diffusing cations can produce many similar styles of surface textural changes; and (3) the main difference between abiotic and biotically produced weathering is the scale (microns versus nanometers) and the style (crystallographically versus noncrystallographically controlled) of the textural features. Further investigation into nanosize scale surface textures should attempt to quantify both textures and chemical changes of the role of microorganisms in the weathering of silicates. Additional experiments addressing nanoscale textures of shock features for comparison with the current data set.

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


    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. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

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


    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…

  18. Stress inhibition of melatonin synthesis in the pineal organ of rainbow trout (Oncorhynchus mykiss) is mediated by cortisol. (United States)

    López-Patiño, Marcos A; Gesto, Manuel; Conde-Sieira, Marta; Soengas, José L; Míguez, Jesús M


    Cortisol has been suggested to mediate the effect of stress on pineal melatonin synthesis in fish. Therefore, we aimed to determine how pineal melatonin synthesis is affected by exposing rainbow trout to different stressors, such as hypoxia, chasing and high stocking density. In addition, to test the hypothesis that cortisol is a mediator of such stress-induced effects, a set of animals were intraperitoneally implanted with coconut oil alone or containing cortisol (50 mg kg(-1) body mass) and sampled 5 or 48 h post-injection at midday and midnight. The specificity of such effect was also assessed in cultured pineal organs exposed to cortisol alone or with the general glucocorticoid receptor antagonist, mifepristone (RU486). Stress (in particular chasing and high stocking density) affected the patterns of plasma and pineal organ melatonin content during both day and night, with the greatest reduction occurring at night. The decrease in nocturnal melatonin levels in the pineal organ of stressed fish was accompanied by increased serotonin content and decreased AANAT2 enzymatic activity and mRNA abundance. Similar effects on pineal melatonin synthesis to those elicited by stress were observed in trout implanted with cortisol for either 5 or 48 h. These data indicate that stress negatively influences the synthesis of melatonin in the pineal organ, thus attenuating the day-night variations of circulating melatonin. The effect might be mediated by increased cortisol, which binds to trout pineal organ-specific glucocorticoid receptors to modulate melatonin rhythms. Our results in cultured pineal organs support this. Considering the role of melatonin in the synchronization of daily and annual rhythms, the results suggest that stress-induced alterations in melatonin synthesis could affect the availability of fish to integrate rhythmic environmental information.

  19. Graphic organizers and their effects on the reading comprehension of students with LD: a synthesis of research. (United States)

    Kim, Ae-Hwa; Vaughn, Sharon; Wanzek, Jeanne; Wei, Shangjin


    Previous research studies examining the effects of graphic organizers on reading comprehension for students with learning disabilities (LD) are reviewed. An extensive search of the professional literature between 1963 and June 2001 yielded a total of 21 group design intervention studies that met the criteria for inclusion in the synthesis. Using graphic organizers (i.e., semantic organizers, framed outlines, cognitive maps with and without a mnemonic) was associated with improved reading comprehension overall for students with LD. Compared to standardized reading measures, researcher-developed comprehension measures were associated with higher effect sizes. Initial gains demonstrated when using graphic organizers were not revealed during later comprehension tasks or on new comprehension tasks.

  20. Facile synthesis of multiple enzyme-containing metal-organic frameworks in a biomolecule-friendly environment. (United States)

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


    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.

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

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


    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. Cerium-based metal organic frameworks with UiO-66 architecture: synthesis, properties and redox catalytic activity. (United States)

    Lammert, Martin; Wharmby, Michael T; Smolders, Simon; Bueken, Bart; Lieb, Alexandra; Lomachenko, Kirill A; Vos, Dirk De; Stock, Norbert


    A series of nine Ce(iv)-based metal organic frameworks with the UiO-66 structure containing linker molecules of different sizes and functionalities were obtained under mild synthesis conditions and short reaction times. Thermal and chemical stabilities were determined and a Ce-UiO-66-BDC/TEMPO system was successfully employed for the aerobic oxidation of benzyl alcohol.

  3. Microwave-Enhanced Organic Syntheses for the Undergraduate Laboratory: Diels-Alder Cycloaddition, Wittig Reaction, and Williamson Ether Synthesis (United States)

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


    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…

  4. Facile synthesis of one-dimensional organometallic-organic hybrid polymers based on a diphosphorus complex and flexible bipyridyl linkers. (United States)

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


    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.

  5. Influence of biotic and abiotic factors on metallothionein level in Gammarus pulex. (United States)

    Geffard, A; Quéau, H; Dedourge, O; Biagianti-Risboug, S; Geffard, O


    Detection and assessment of the impact of pollution on biological resources imply increasing research on early-warning markers such as metallothioneins in metal exposure. Metallothioneins are cytosolic, low molecular weight proteins, involved principally in essential metal homeostasis and non-essential metal detoxication. Metallothionein synthesis could be influenced by abiotic (season) or biotic (reproduction process) factors directly or indirectly by its effect on metal bioaccumulation (i.e., sex, weight). In a view of using metallothioneins as metal-exposure biomarkers in Gammarus pulex, this study attempts to define the effect of several factors (sex, weight/size and season) on the level of this protein. Metallothionein levels recorded in individuals over a large range of weights indicate a negative correlation between them. Inversely in our conditions, no difference was observed between male and female organisms. During field study, metallothionein level changes were observed with the highest levels in autumn and winter periods. The highest metallothionein levels were observed after the reproduction period, perhaps linked with the metabolic needs of biologically available essential metal such as zinc.

  6. Synthesis and Structural Characterization of Carboxylate-Based Metal-Organic Frameworks and Coordination Networks (United States)

    Calderone, Paul

    Coordination networks (CNs) and metal-organic frameworks (MOFs) are crystalline materials composed of metal ions linked by multifunctional organic ligands. From these connections, infinite arrays of one-, two-, or three-dimensional networks can be formed. Exploratory synthesis and research of novel CNs and MOFs is of current interest because of their many possible industrial applications including gas storage, catalysis, magnetism, and luminescence. A variety of metal centers and organic ligands can be used to synthesize MOFs and CNs under a range of reaction conditions, leading to extraordinary structural diversity. The characteristics of the metals and linkers, such as properties and coordination preferences, play the biggest role in determining the structure and properties of the resulting network. Thus, the choice of metal and linker is dictated by the desired traits of the target network. The pervasive use of transition metal centers in MOF synthesis stems from their well-known coordination behavior with carboxylate-based linkers, thus facilitating design strategies. Conversely, CNs and MOFs based on s-block and lanthanide metals are less studied because each group presents unique challenges to structure prediction. Lanthanide metals have variable coordination spheres capable of accommodating up to twelve atoms, while the bonding in s-block metals takes on a mainly ionic character. In spite of these obstacles, lanthanide and s-block CNs are worthwhile synthetic targets because of their unique properties. Interesting photoluminescent and sensing materials can be developed using lanthanide metals, whereas low atomic weight s-block metals may afford an advantage in gravimetric advantages for gas storage applications. The aim of this research was to expand the current understanding of carboxylate-based CN and MOF synthesis by varying the metals, solvents, and temperatures used. To this end, magnesium-based CNs were examined using a variety of aromatic carboxylate

  7. Organic luminescent materials. First results on synthesis and characterization of Alq{sub 3} thin films

    Energy Technology Data Exchange (ETDEWEB)

    Baldacchini, G.; Gagliardi, S.; Montereali, R.M.; Pace, A. [ENEA, Centro Ricerche Frascati, Frascati, RM (Italy). Div. Fisica Applicata; Balaji Pode, R. [Nagpur University, Nagpur (India). Dept. of Physics


    Inorganic semiconductor diodes brought a technological revolution in the field of efficient light and laser sources in the last 20 years. New development in this field are expected from organic compounds, thanks to their low cost of synthesis and the relative easiness of growth as thin films. In particular, electrically pumped luminescent devices based on organic thin layers are among the most promising systems for next generation flat panel displays and semiconductor lasers. The tris - (8-hydroxy quinoline)-aluminium complex-Alq{sub 3} - is one of the most studied electro luminescent materials. In this paper, after a short introduction regarding historical development in the field, are reported preliminary results on the growth of Alq{sub 3} films and on their optical and spectroscopic characterization. [Italian] Negli ultimi 20 anni i diodi semiconduttori hanno portato una rivoluzione tecnologica nel campo delle sorgenti luminose e laser. Un nuovo sviluppo possibile in questo campo sono i composti organici, grazie al basso costo di sintesi e la relativa facilita' di crescerli in forma di film sottile. In particolare, dispositivi luminescenti pompati elettricamente basati su film sottili di materiali organici sono promettenti per una nuova generazione di display per schermi piatti e laser a Alq{sub 3} e' uno dei materiali elettroluminescenti piu' studiati. In questo rapporto, dopo una breve introduzione sullo sviluppo storico in questo campo, presentiamo i nostri primi risultati sulla crescita e caratterizzazione ottica di film di Alq{sub 3}.

  8. Bulk synthesis of metal-organic hybrid dimers and their propulsion under electric fields. (United States)

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


    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.

  9. A New Energy Source for Organic Synthesis in Europa's Surface Ice (United States)

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


    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.

  10. Geometric Shape Regulation and Noncovalent Synthesis of One-Dimensional Organic Luminescent Nano-/Micro-Materials. (United States)

    Song, Xiaoxian; Zhang, Zuolun; Zhang, Shoufeng; Wei, Jinbei; Ye, Kaiqi; Liu, Yu; Marder, Todd B; Wang, Yue


    Noncovalent synthesis of one-dimensional (1D) organic nano-/micro-materials with controllable geometric shapes or morphologies and special luminescent and electronic properties is one of the greatest challenges in modern chemistry and material science. Control of noncovalent interactions is fundamental for realizing desired 1D structures and crucial for understanding the functions of these interactions. Here, a series of thiophene-fused phenazines composed of a halogen-substituted π-conjugated plate and a pair of flexible side chains is presented, which displays halogen-dependent 1D self-assemblies. Luminescent 1D twisted wires, straight rods, and zigzag wires, respectively, can be generated in sequence when the halogen atoms are varied from the lightest F to the heaviest I. It was demonstrated that halogen-dependent anisotropic noncovalent interactions and mirror-symmetrical crystallization dominated the 1D-assembly behaviors of this class of molecules. The methodology developed in this study provides a potential strategy for constructing 1D organic materials with unique optoelectronic functions.

  11. Family perspectives on deceased organ donation: thematic synthesis of qualitative studies. (United States)

    Ralph, A; Chapman, J R; Gillis, J; Craig, J C; Butow, P; Howard, K; Irving, M; Sutanto, B; Tong, A


    A major barrier to meeting the needs for organ transplantation is family refusal to give consent. This study aimed to describe the perspectives of donor families on deceased donation. We conducted a systematic review and thematic synthesis of qualitative studies. Electronic databases were searched to September 2012. From 34 studies involving 1035 participants, we identified seven themes: comprehension of sudden death (accepting finality of life, ambiguity of brain death); finding meaning in donation (altruism, letting the donor live on, fulfilling a moral obligation, easing grief); fear and suspicion (financial motivations, unwanted responsibility for death, medical mistrust); decisional conflict (pressured decision making, family consensus, internal dissonance, religious beliefs); vulnerability (valuing sensitivity and rapport, overwhelmed and disempowered); respecting the donor (honoring the donor's wishes, preserving body integrity) and needing closure (acknowledgment, regret over refusal, unresolved decisional uncertainty, feeling dismissed). Bereaved families report uncertainty about death and the donation process, emotional and cognitive burden and decisional dissonance, but can derive emotional benefit from the "lifesaving" act of donation. Strategies are needed to help families understand death in the context of donation, address anxieties about organ procurement, foster trust in the donation process, resolve insecurities in decision making and gain a sense of closure. © Copyright 2014 The American Society of Transplantation and the American Society of Transplant Surgeons.

  12. Microwave Assisted Organic Synthesis of Heterocycles in Aqueous Media: Recent Advances in Medicinal Chemistry. (United States)

    Frecentese, Francesco; Saccone, Irene; Caliendo, Giuseppe; Corvino, Angela; Fiorino, Ferdinando; Magli, Elisa; Perissutti, Elisa; Severino, Beatrice; Santagada, Vincenzo


    Green chemistry is a discipline of great interest in medicinal chemistry. It involves all fields of chemistry and it is based on the principle to conduct chemical reactions protecting the environment at the same time, through the use of chemical procedures able to avoid pollution. In this context, water as solvent is a good choice because it is abundant, nontoxic, non-caustic, and non-combustible. Even if microwave assisted organic reactions in conventional solvents have quickly progressed, in the recent years medicinal chemists have focused their attention to processes deemed not dangerous for the environment, using nanotechnology and greener solvents as water. Several reports of reaction optimizations and selectivities, demonstrating the capability of microwave to allow the obtaining of increased yields have been recently published using water as solvent. In this review, we selected the available knowledge related to microwave assisted organic synthesis in aqueous medium, furnishing examples of the newest strategies to obtain useful scaffolds and novel derivatives for medicinal chemistry purposes. The intention of this review is to demonstrate the exclusive ability of MAOS in water as solvent or as co-solvent. For this purpose we report here the most representative applications of MAOS using water as solvent, focusing on medicinal chemistry processes leading to interesting nitrogen containing heterocycles with potential pharmaceutical applications.

  13. Ultrasound assisted synthesis of amide functionalized metal-organic framework for nitroaromatic sensing. (United States)

    Gharib, Maniya; Safarifard, Vahid; Morsali, Ali


    Nano plates of zinc(II) based metal-organic framework (MOF) were prepared via ultrasonic method without any surfactants at room temperature and atmospheric pressure. Control of particle size and morphology was enhanced in this synthesis method. Nano plates of an interpenetrated amide-functionalized metal-organic framework, [Zn 2 (oba) 2 (bpfb)]·(DMF) 5 , TMU-23, (H 2 oba = 4,4'-oxybis(benzoic acid); bpfb = N,N'-bis-(4-pyridylformamide)-1,4-benzenediamine, DMF = N,N-dimethyl formamide), was synthesized under ultrasound irradiation in different concentrations of initial precursor. The nano structure and morphology of the synthesized MOF were characterized by Field Emission Scanning Electron Microscopy (FE-SEM), powder X-ray diffraction, thermo gravimetric analysis (TGA), elemental analysis and FTIR spectroscopy. Moreover, Fluorescence emissions of nanoplates have been studied. Amide-functionalized MOF shows high selectivity for sensing of nitroaromatic compounds such as nitrophenol, nitroaniline, and nitrobenzene in acetonitrile solution. Fluorescence intensity decreased with increasing contents of nitroaromatics in acetonitrile solution due to fluorescence quenching effect. Copyright © 2017 Elsevier B.V. All rights reserved.

  14. Synthesis of scintillating metal organic frameworks for the detection of radiation from subatomic particles (United States)

    Ingram, Conrad; Williams, Michael


    The objective of this research is to develop fluorescent metal organic frameworks (MOFs) as scintillation materials for more efficient light output and detection of ionizing radiation, such as neutrons, alpha particles or gamma rays, generated by fissile materials. MOFs are multidimensional porous structures, which are synthesized from the covalent bonding of metal ions or metal oxide clusters with organic ligand linkers, such as benzene dicarboxylates. The ligands will be chosen to have fluorescent characteristics, when excited by radiation or energetic sub-atomic particles. We will explore the synthesis of new MOFs, containing carboxylate ligands with unique conjugated chromophores, such as, benzene-1,3,5-triyltris(ethene-2,1-diyl)) tribenzoic acid and 9-hydroxy-9-vinyl-9H-fluorene-2,7-dicarboxylic acid), and doped with heavy metal as triplet-state harvesters, that we are proposing will result in stronger and possibly, unique luminescence spectral features that will allow for the discrimination between different ionizing radiations from subatomic particles. Photo-, catho- and radio-luminescence studies will be conducted on the materials, and radiation mechanism(s) will be investigated.

  15. Abiotic drivers of Chihuahuan Desert plant communities (United States)

    Laura Marie Ladwig


    Within grasslands, precipitation, fire, nitrogen (N) addition, and extreme temperatures influence community composition and ecosystem function. The differential influences of these abiotic factors on Chihuahuan Desert grassland communities was examined within the Sevilleta National Wildlife Refuge, located in central New Mexico, U.S.A. Although fire is a natural...

  16. Does disease-irrelevant intrathecal synthesis in multiple sclerosis make sense in the light of tertiary lymphoid organs?

    Directory of Open Access Journals (Sweden)

    Mickael eBonnan


    Full Text Available Although partly disease-irrelevant, intrathecal Ig synthesis is a typical feature of multiple sclerosis (MS and is driven by the tertiary lymphoid organs (TLO. A long-known hallmark of this non-specific intrathecal synthesis is the MRZ pattern, an intrathecal synthesis of Ig against measles, rubella and zoster viruses, which could also be involved in a wide range of pathogens. However, this non-specific synthesis is highly problematic since brain TLO should not be able to drive the clonal expansion of lymphocytes against alien antigens that are thought to be absent in MS brain.We propose to explain the paradox of non-specific intrathecal synthesis by discussing the natural properties of TLO. In fact, besides local antigen-driven clonal expansion, circulating plasmablasts and plasma cells (PC are non-specifically recruited from blood and gain access to survival niches in the inflammatory CNS. This mechanism, which has been described in other inflammatory disorders, takes place in the TLO. As a consequence, PCs recruited in brain mirror the individual’s history of immunization and intrathecal synthesis of IgG in MS may target a broad range of common infectious agents, a hypothesis in line with epidemiological data. Moreover, the immunization schedule and its timing may interfere with PC recruitment. If this hypothesis is correct, the reaction against EBV appears paradoxical: although early infection of MS patients is systematic, intrathecal synthesis is far lower than expected, suggesting a crucial interaction between MS onset and timing of EBV infection. A growing body of evidence suggests that the non-specific intrathecal synthesis observed in MS is also common in many chronic CNS inflammatory disorders. Assuming that cortical TLO in MS are associated with typical sub-pial lesions, we have coined the concept of ‘TLO-pathy’ to describe these lesions and take examples of them from non-MS disorders.

  17. Greening the Processes of Metal-Organic Framework Synthesis and their Use in Sustainable Catalysis. (United States)

    Chen, Junying; Shen, Kui; Li, Yingwei


    Given the shortage of sustainable resources and the increasingly serious environmental issues in recent decades, the demand for clean technologies and sustainable feedstocks is of great interest to researchers worldwide. With regard to the fields of energy saving and environmental remediation, the key point is the development of efficient catalysts, not only in terms of facile synthesis methods, but also the benign utilization of such catalysts. This work reviews the use of metal-organic frameworks (MOFs) and MOF-based materials in these fields. The definition of MOFs and MOF-based materials will be primarily introduced followed by a brief description of the characterization and stability of MOF-related materials under the applied conditions. The greening of MOF synthesis processes will then be discussed and catalogued by benign solvents and conditions and green precursors of MOFs. Furthermore, their suitable application in sustainable catalysis will be summarized, focusing on several typical atom-economic reactions, such as the direct introduction of H 2 or O 2 and C-C bond formation. Approaches towards reducing CO 2 emission by MOF-based catalysts will be described with special emphasis on CO 2 fixation and CO 2 reduction. In addition, driven by the explosive growth of energy consumption in the last century, much research has gone into biomass, which represents a renewable alternative to fossil fuels and a sustainable carbon feedstock for chemical production. The advanced progress of biomass-related transformations is also illustrated herein. Fundamental insights into the nature of MOF-based materials as constitutionally easily recoverable heterogeneous catalysts and as supports for various active sites is thoroughly discussed. Finally, challenges facing the development of this field and the outlook for future research are presented. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Synthesis of Thin Film Composite Metal-Organic Frameworks Membranes on Polymer Supports

    KAUST Repository

    Barankova, Eva


    Since the discovery of size-selective metal-organic frameworks (MOF) researchers have tried to manufacture them into gas separation membranes. ZIF-8 became the most studied MOF for membrane applications mainly because of its simple synthesis, good chemical and thermal stability, recent commercial availability and attractive pore size. The aim of this work is to develop convenient methods for growing ZIF thin layers on polymer supports to obtain defect-free ZIF membranes with good gas separation properties. We present new approaches for ZIF membranes preparation on polymers. We introduce zinc oxide nanoparticles in the support as a secondary metal source for ZIF-8 growth. Initially the ZnO particles were incorporated into the polymer matrix and later on the surface of the polymer by magnetron sputtering. In both cases, the ZnO facilitated to create more nucleation opportunities and improved the ZIF-8 growth compared to the synthesis without using ZnO. By employing the secondary seeded growth method, we were able to obtain thin (900 nm) ZIF-8 layer with good gas separation performance. Next, we propose a metal-chelating polymer as a suitable support for growing ZIF layers. Defect-free ZIF-8 films with a thickness of 600 nm could be obtained by a contra-diffusion method. ZIF-8 membranes were tested for permeation of hydrogen and hydrocarbons, and one of the highest selectivities reported so far for hydrogen/propane, and propylene/propane was obtained. Another promising method to facilitate the growth of MOFs on polymeric supports is the chemical functionalization of the support surface with functional groups, which can complex metal ions and which can covalently bond the MOF crystals. We functionalized the surface of a common porous polymeric membrane with amine groups, which took part in the reaction to form ZIF-8 nanocrystals. We observed an enhancement in adhesion between the ZIF layer and the support. The effect of parameters of the contra-diffusion experiment

  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)


    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. One-pot green synthesis of zinc oxide nano rice and its application as sonocatalyst for degradation of organic dye and synthesis of 2-benzimidazole derivatives (United States)

    Paul, Bappi; Vadivel, Sethumathavan; Dhar, Siddhartha Sankar; Debbarma, Shyama; Kumaravel, M.


    In this paper, we report novel and green approach for one-pot biosynthesis of zinc oxide (ZnO) nanoparticles (NPs). Highly stable and hexagonal phase ZnO nanoparticles were synthesized using seeds extract from the tender pods of Parkia roxburghii and characterized by XRD, FT-IR, EDX, TEM, and N2 adsorption-desorption (BET) studies. The present method of synthesis of ZnO NPs is very efficient and cost effective. The powder XRD pattern furnished evidence for the formation of hexagonal close packing structure of ZnO NPs having average crystallite size 25.6 nm. The TEM image reveals rice shapes ZnO NPs are with an average diameter of 40-60 nm. The as-synthesized ZnO NPs has proved to be an excellent sonocatalysts for degradation of organic dye and synthesis of 2-benzimidazole derivatives.

  1. 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.


    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

  2. Resilience of cereal crops to abiotic stress: A review | Ahmad ...

    African Journals Online (AJOL)

    Therefore, breeding for abiotic stress tolerance in crop plants should be given high research priority as abiotic stresses are the main factor negatively affecting crop growth and productivity ... Keywords: Cereal crops, abiotic stresses, food insecurity, molecular breeding, quantitative trait loci (QTLs), salinity, water stress.

  3. 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.


    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

  4. Organic Synthesis and Potential Microbiology in the Solar Nebula: Are Early Solar Systems Nurseries for Microorganisms? (United States)

    Mautner, M. N.; Ibrahim, Y.; El-Shall, M. S.


    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 2. M. Mautner and G. L. Matloff, Directed Panspermia...., Bull

  5. Designed synthesis of nanoporous organic polymers for selective gas uptake and catalytic applications (United States)

    Arab, Pezhman

    Design and synthesis of porous organic polymers have attracted considerable attentions during the past decade due to their wide range of applications in gas storage, gas separation, energy conversion, and catalysis. Porous organic polymers can be pre-synthetically and post-synthetically functionalized with a wide variety of functionalities for desirable applications. Along these pursuits, we introduced new synthetic strategies for preparation of porous organic polymers for selective CO2 capture and catalytic applications. Porous azo-linked polymers (ALPs) were synthesized by an oxidative reaction of amine-based monomers using copper(I) as a catalyst which leads to azo-linkage formation. ALPs exhibit high surface areas of up to 1200 m2 g-1 and have high chemical and thermal stabilities. The nitrogen atoms of the azo group can act as Lewis bases and the carbon atom of CO2 can act as a Lewis acid. Therefore, ALPs show high CO2 uptake capacities due to this Lewis acid-based interaction. The potential applications of ALPs for selective CO2 capture from flue gas, natural gas, and landfill gas under pressure-swing and vacuum swing separation settings were studied. Due to their high CO2 uptake capacity, selectivity, and regenerability, ALPs are among the best porous organic frameworks for selective CO2 capture. In our second project, a new bis(imino)pyridine-linked porous polymer (BIPLP-1) was synthesized and post-synthetically functionalized with Cu(BF4)2 for highly selective CO2 capture. BIPLP-1 was synthesized via a condensation reaction between 2,6-pyridinedicarboxaldehyde and 1,3,5-tris(4-aminophenyl)benzene, wherein the bis(imino)pyridine linkages are formed in-situ during polymerization. The functionalization of the polymer with Cu(BF4)2 was achieved by treatment of the polymer with a solution of Cu(BF4)2 via complexation of copper cations with bis(imino)pyridine moieties of the polymer. BF4- ions can act Lewis base and CO2 can act as a Lewis acid; and therefore

  6. Oxide-based inorganic/organic and nanoporous spherical particles: synthesis and functional properties

    Directory of Open Access Journals (Sweden)

    Kota Shiba, Motohiro Tagaya, Richard D Tilley and Nobutaka Hanagata


    Full Text Available This paper reviews the recent progress in the preparation of oxide-based and heteroatom-doped particles. Surfactant-templated oxide particles, e.g. silica and titania, are possible candidates for various potential applications such as adsorbents, photocatalysts, and optoelectronic and biological materials. We highlight nanoporous oxides of one element, such as silicon or titanium, and those containing multiple elements, which exhibit properties that are not achieved with individual components. Although the multicomponent nanoporous oxides possess a number of attractive functions, the origin of their properties is hard to determine due to compositional/structural complexity. Particles with a well-defined size and shape are keys for a quantitative and detailed discussion on the unique complex properties of the particles. From this viewpoint, we review the synthesis techniques of the oxide particles, which are functionalized with organic molecules or doped with heteroatoms, the physicochemical properties of the particles and the possibilities for their photofunctional applications as complex systems.

  7. 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


    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.

  8. 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)


    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.

  9. Layered cobalt hydroxysulfates with both rigid and flexible organic pillars: synthesis, structure, porosity, and cooperative magnetism. (United States)

    Rujiwatra, A; Kepert, C J; Claridge, J B; Rosseinsky, M J; Kumagai, H; Kurmoo, M


    The synthesis and characterization of two members of a family of porous magnetic materials is described. The structures of Co4(SO4)(OH)6(C2N2H8)0.5*3H2O and Co4(SO4)(OH)6(C6N2H12)0.5*H2O and their thermal stability can be tailored via the choice of organic pillar. The interactions between the pillaring agent and the compositionally complex inorganic layer are discussed. The influences of two pillaring agents i.e., the flexible ethylenediamine and the relatively rigid 1,4-diazabicyclo[2,2,2]octane, on thermal stability, rigidity upon guest loss, and magnetic behavior of the pillared solids are compared. The magnetism of the pillared layered cobalt hydroxides is complex due to the influences of multiple metal sites, inter- and intralayer exchange, spin-orbit coupling, and geometrical frustration. The wide variety of potential pillars, oxyanions, and possible metal substitutions at the octahedral and tetrahedral sites offers the possibility of tailoring the magnetic and porous properties of these materials.

  10. Metal organic framework synthesis in the presence of surfactants: towards hierarchical MOFs? (United States)

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


    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 MOF with hierarchical pore structure. Depending on the pH and the solvent used, different topologies were obtained (namely, MIL-96, MIL-100 and MIL-110). On the one hand, MIL-110 was obtained at lower temperatures than those commonly reported in the literature and without additives to control the pH; on the other hand, MIL-100 with crystallite sizes as small as 30 ± 10 nm could be easily synthesized in a mixture of H2O and EtOH with a H2O/EtOH molar ratio of 3.4 at pH 2.6 in the presence of CTAB. The resulting material displays a hierarchical porosity that combines the microporosity from the MOF and the non-ordered mesopores defined in between the MOF nanoparticles. Interestingly, the maximum of the pore size distribution could be varied between 3 and 33 nm. Finally, at pH 2.5 and using water as a solvent, platelets of MIL-96, a morphology never observed before for this MOF, were synthesized with a (001) preferential crystal orientation, the (001) plane running parallel to the bipyramidal cages of the MIL-96 topology.

  11. Preparation of fluorescent DNA probe by solid-phase organic synthesis

    Directory of Open Access Journals (Sweden)


    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.

  12. Design and Synthesis of Biomimetic Hydrogel Scaffolds with Controlled Organization of Cyclic RGD Peptides (United States)

    Zhu, Junmin; Tang, Chad; Kottke-Marchant, Kandice; Marchant, Roger E.


    We report on the rational design and synthesis of a new type of bioactive poly(ethylene glycol) diacrylate (PEGDA) macromers, cyclic Arg-Gly-Asp (cRGD)-PEGDA, to mimic the cell-adhesive properties of extracellular matrix (ECM), aiming to create biomimetic scaffolds with controlled spatial organization of ligands and enhanced cell binding affinity for tissue engineering. To attach the cRGD peptide in the middle of PEGDA chain, a tailed cRGD peptide, c[RGDfE(SSSKK-NH2)] (1) was synthesized with c(RGDfE) linked to a tail of SSSKK. The tail consists of a spacer with three serine residues, and a linker with two lysine residues for conjugating with acryloyl-PEG-NHS (5) to create cRGD-PEGDA (6). cRGD-PEGDA possesses good ability of photopolymerization to fabricate hydrogel scaffolds under UV radiation. Surface morphology and composition analysis demonstrates that cRGD-PEGDA hydrogels were well-constructed with porous three-dimensional (3D) structures and uniform distribution of cRGD ligands. Our results show that cRGD-PEGDA hydrogels facilitate endothelial cell (EC) adhesion and spreading on the hydrogel surfaces, and exhibit significantly higher EC population in comparison with linear RGD-modified hydrogels at low peptide incorporation. Since ligand presentation in biomimetc scaffolds plays an important role in controlling cell behaviors, cRGD-PEGDA has great advantages of controlling hydrogel properties and ligand spatial organization in the resulting scaffolds. Furthermore, cRGD-PEGDA is an attractive candidate for the future development of tissue engineering scaffolds with optimum cell adhesive strength and ligand density. PMID:19191566

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

    Directory of Open Access Journals (Sweden)

    Xiao-Min eLiu


    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.

  14. Improving abiotic stress tolerance of quinoa

    DEFF Research Database (Denmark)

    Yang, Aizheng

    other crops, its productivity declines under severe drought, high salt conditions and harsh climate conditions. Different management approaches including water-saving irrigation methods (such as deficit irrigation, DI and alternate root-zone drying irrigation, ARD), inoculating crop seeds with plant......Global food security faces the challenges of rapid population growth and shortage of water resources. Drought, heat waves and soil salinity are becoming more frequent and extreme due to climatic changes in many regions of the world, and resulting in yield reduction of many crops. It is hypothesized...... that quinoa has the potential to grow under a range of abiotic stresses, tolerating levels regarded as stresses in other crop species. Therefore cultivation of quinoa (Chenopodium quinoa Willd.) could be an alternative option in such regions. Even though quinoa is more tolerant to abiotic stress than most...

  15. Utilização do D-manitol em síntese orgânica D-Mannitol in Organic Synthesis

    Directory of Open Access Journals (Sweden)

    Pedro S. M. de Oliveira


    Full Text Available D-mannitol is used in several fields including food, pharmaceuticals, cosmetics and textiles being an important carbohydrate found widespread in nature. Due to its chirality, it is largely used in organic synthesis with several applications, such as ligands, polymers, chiral pool, for preparation of small chiral building blocks, key intermediates in total synthesis. In this context, the aim of this review is to highlights recent applications of D-mannitol, especially in total synthesis.

  16. Abiotic factors influencing tropical dry forests regeneration

    Directory of Open Access Journals (Sweden)

    Ceccon Eliane


    Full Text Available Tropical dry forests represent nearly half the tropical forests in the world and are the ecosystems registering the greatest deterioration from the anthropogenic exploitation of the land. This paper presents a review on the dynamics of tropical dry forests regeneration and the main abiotic factors influencing this regeneration, such as seasonal nature, soil fertility and humidity, and natural and anthropic disturbances. The main purpose is to clearly understand an important part of TDF succession dynamics.

  17. Role of sugars under abiotic stress. (United States)

    Sami, Fareen; Yusuf, Mohammad; Faizan, Mohammad; Faraz, Ahmad; Hayat, Shamsul


    Sugars are the most important regulators that facilitate many physiological processes, such as photosynthesis, seed germination, flowering, senescence, and many more under various abiotic stresses. Exogenous application of sugars in low concentration promote seed germination, up regulates photosynthesis, promotes flowering, delayed senescence under various unfavorable environmental conditions. However, high concentration of sugars reverses all these physiological process in a concentration dependent manner. Thus, this review focuses the correlation between sugars and their protective functions in several physiological processes against various abiotic stresses. Keeping in mind the multifaceted role of sugars, an attempt has been made to cover the role of sugar-regulated genes associated with photosynthesis, seed germination and senescence. The concentration of sugars determines the expression of these sugar-regulated genes. This review also enlightens the interaction of sugars with several phytohormones, such as abscisic acid, ethylene, cytokinins and gibberellins and its effect on their biosynthesis under abiotic stress conditions. Copyright © 2016 Elsevier Masson SAS. All rights reserved.

  18. Poly(ethylene glycol)-based ionic liquids: properties and uses as alternative solvents in organic synthesis and catalysis. (United States)

    Cecchini, Martina Maya; Charnay, Clarence; De Angelis, Francesco; Lamaty, Frédéric; Martinez, Jean; Colacino, Evelina


    PEG-based ionic liquids are a new appealing group of solvents making the link between two distinct but very similar fluids: ionic liquids and poly(ethylene glycol)s. They find applications across a range of innumerable disciplines in science, technology, and engineering. In the last years, the possibility to use these as alternative solvents for organic synthesis and catalysis has been increasingly explored. This Review highlights strategies for their synthesis, their physical properties (critical point, glass transition temperature, density, rheological properties), and their application in reactions catalyzed by metals (such as Pd, Cu, W, or Rh) or as organic solvent (for example for multicomponent reactions, organocatalysis, CO2 transformation) with special emphasis on their toxicity, environmental impact, and biodegradability. These aspects, very often neglected, need to be considered in addition to the green criteria usually considered to establish ecofriendly processes. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. 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


    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....../acceptor fitting within the polymer, side chains to ensure solubility and HOMO/LUMO level alignment with the acceptor (e.g. [60]PCBM) to take into consideration.......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...

  20. Optimized synthesis and crystalline stability of γ-cyclodextrin metal-organic frameworks for drug adsorption. (United States)

    Liu, Botao; Li, Haiyan; Xu, Xiaonan; Li, Xue; Lv, Nana; Singh, Vikramjeet; Stoddart, J Fraser; York, Peter; Xu, Xu; Gref, Ruxandra; Zhang, Jiwen


    The biocompatible and renewable cyclodextrin metal-organic frameworks (CD-MOFs) have addressed a range of opportunities in molecular storage and separation sciences. The reported protocols for their synthesis, however, were carried out at room temperature over long time periods of time (24h), producing crystals of relatively poor uniformity. In this investigation, micron sized γ-CD-MOFs were synthesized by an optimized vapor diffusion method at elevated temperature (50°C) within 6h, after which the size control, crystalline stability and drug adsorption behavior were investigated in detail. In this manner, uniform cubic γ-CD-MOF crystals were obtained when the reaction temperature was raised to 50°C with pre-addition of the reaction solvent. The size of γ-CD-MOFs was adjusted efficiently by changing the reactant concentrations, temperatures, time, γ-CD ratios to KOH and surfactant concentrations, without influencing the porosity and crystallinity of the material markedly. Varing degrees of reduction in crystallinity and change in morphology were observed when the γ-CD-MOF crystals are treated under conditions of high temperature (100°C), high humidity (92.5%) and polar solvents (e.g., MeOH and DMF). In relation to drug adsorption by γ-CD-MOFs, most of the drug molecules containing carboxyl groups showed relatively high adsorption (>5%), while low adsorption (<5%) was found for drugs with nitrogen-containing heterocyclic rings. In addition, the adsorption kinetics of captopril to standard γ-CD-MOFs matched a pseudo-second-order model rather well, whilst captopril adsorption to the damaged γ-CD-MOFs only partially matched the pseudo-second-order model. In summary, based upon the optimized synthesis and size control of γ-CD-MOFs, the crystalline stability and drug adsorption characteristics of γ-CD-MOF crystals have been evaluated as a fundamental requirement of a potential vehicle for drug delivery. Copyright © 2016 Elsevier B.V. All rights reserved.

  1. Synthesis and characterization of bimetallic metal-organic framework Cu-Ru-BTC with HKUST-1 structure. (United States)

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


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

  2. Hierarchical Metal-Organic Framework Hybrids: Perturbation-Assisted Nanofusion Synthesis. (United States)

    Yue, Yanfeng; Fulvio, Pasquale F; Dai, Sheng


    Metal-organic frameworks (MOFs) represent a new family of microporous materials; however, microporous-mesoporous hierarchical MOF materials have been less investigated because of the lack of simple, reliable methods to introduce mesopores to the crystalline microporous particles. State-of-the-art MOF hierarchical materials have been prepared by ligand extension methods or by using a template, resulting in intrinsic mesopores of longer ligands or replicated pores from template agents, respectively. However, mesoporous MOF materials obtained through ligand extension often collapse in the absence of guest molecules, which dramatically reduces the size of the pore aperture. Although the template-directed strategy allows for the preparation of hierarchical materials with larger mesopores, the latter requires a template removal step, which may result in the collapse of the implemented mesopores. Recently, a general template-free synthesis of hierarchical microporous crystalline frameworks, such as MOFs and Prussian blue analogues (PBAs), has been reported. This new method is based on the kinetically controlled precipitation (perturbation), with simultaneous condensation and redissolution of polymorphic nanocrystallites in the mother liquor. This method further eliminates the use of extended organic ligands and the micropores do not collapse upon removal of trapped guest solvent molecules, thus yielding hierarchical MOF materials with intriguing porosity in the gram scale. The hierarchical MOF materials prepared in this way exhibited exceptional properties when tested for the adsorption of large organic dyes over their corresponding microporous frameworks, due to the enhanced pore accessibility and electrolyte diffusion within the mesopores. As for PBAs, the pore size distribution of these materials can be tailored by changing the metals substituting Fe cations in the PB lattice. For these, the textural mesopores increased from approximately 10 nm for Cu analogue (meso

  3. 'Dialyzable' Carbosilane Dendrimers as Soluble Supports in Organic Synthesis: Proof of principle, application and diafiltration performance

    NARCIS (Netherlands)

    Wander, M.


    Since the development of polystyrene as (insoluble) support for the synthesis of peptides by Merrifield in the 1960s, the application of supported synthesis in both industrial and academic research has increased. The introduction of dendrimers as supports solved many of the problems arising from the

  4. Hydrothermal Synthesis and Characterization of a Metal-Organic Framework by Thermogravimetric Analysis, Powder X-Ray Diffraction, and Infrared Spectroscopy: An Integrative Inorganic Chemistry Experiment (United States)

    Crane, Johanna L.; Anderson, Kelly E.; Conway, Samantha G.


    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)…

  5. Supercritical hydrothermal synthesis and in situ organic modification of indium tin oxide nanoparticles using continuous-flow reaction system. (United States)

    Lu, Jinfeng; Minami, Kimitaka; Takami, Seiichi; Shibata, Masatoshi; Kaneko, Yasunobu; Adschiri, Tadafumi


    ITO nanoparticles were synthesized hydrothermally and surface modified in supercritical water using a continuous flow reaction system. The organic modification of the nanoparticles converted the surface from hydrophilic to hydrophobic, making the modified nanoparticles easily dispersible in organic solvent. The addition of a surface modifier into the reaction system impacted the crystal growth and particle size as well as dispersion. The particle size was 18 nm. Highly crystalline cubic ITO with a narrow particle size distribution was obtained. The advantages of short reaction time and the use of a continuous reaction system make this method suitable for industrial scale synthesis. © 2011 American Chemical Society

  6. Correction: An unsymmetrical non-fullerene acceptor: synthesis via direct heteroarylation, self-assembly, and utility as a low energy absorber in organic photovoltaic cells. (United States)

    Payne, Abby-Jo; Li, Shi; Dayneko, Sergey V; Risko, Chad; Welch, Gregory C


    Correction for 'An unsymmetrical non-fullerene acceptor: synthesis via direct heteroarylation, self-assembly, and utility as a low energy absorber in organic photovoltaic cells' by Abby-Jo Payne et al., Chem. Commun., 2017, 53, 10168-10171.

  7. Synthesis of mono-organo-tins and use as versatile reagents for organic synthesis; Synthese de monoorganoetains, nouveaux reactifs pour la synthese organique

    Energy Technology Data Exchange (ETDEWEB)

    Fouquet, E.; Pereyre, M.; Rodriguez, A.L.; Roulet, T. [Bordeaux-1 Univ., 33 (France). Laboratoire de Chimie Organique et Organometallique


    There is a need in researching new methodologies for organic synthesis avoiding polluting or toxic side products. Organo-tin chemistry is particularly concerned by these environmental considerations due to the well-known toxicity of tri-organo-tin residues. In addition to catalytic organo-tin methods or polymer supported organo-tin reagents, mono-organo-tins represent an attracting alternative to the usual tetra-organo-tin chemistry in the sense that after work, tin residues would be inorganic ones. But, the chemistry of mono-organo-tins has not really been exploited so far, mainly due to their high reactivity and to the difficulties in finding general preparation methods. In this work, the direct and quantitative preparation of some mono-organo-tins starting from Lappert`s stannylene represents a general access to a new class of organo-tin reagents. Their reactivity and versatility in the field of organic synthesis is highlighted. The influence of the substituents bound to the tin atom is shown for various reactions such as nucleophilic addition onto carbonyl compounds, radical transfer of functionalized allylic moieties and coupling reactions catalyzed by transition metals. (authors) 26 refs.

  8. Metal-Organic Frameworks: Building Block Design Strategies for the Synthesis of MOFs.

    KAUST Repository

    Luebke, Ryan


    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. Synthesis of complex organic molecules in simulated methane rich astrophysical ices (United States)

    Esmaili, Sasan; Bass, Andrew D.; Cloutier, Pierre; Sanche, Léon; Huels, Michael A.


    It has been proposed that organic molecules required for life on earth may be formed by the radiation processing of molecular ices in space environments, e.g., within our solar system. Such processes can be studied in the laboratory with surface science analytical techniques and by using low-energy electron (LEE) irradiation to simulate the effects of the secondary electrons that are generated in great abundance whenever ionizing radiation interacts with matter. Here we present new measurements of 70 eV LEE irradiation of multilayer films of CH4, 18O2, and CH4/18O2 mixtures (3:1 ratio) at 22 K. The electron stimulated desorption (ESD) yields of cations and anions have been recorded as a function of electron fluence. At low fluence, the prompt desorption of more massive multi-carbon or C—O containing cationic fragments agrees with our earlier measurements. However, new anion ESD signals of C2-, C2H-, and C2H2- from CH4/18O2 mixtures increase with fluence, indicating the gradual synthesis (and subsequent electron-induced fragmentation) of new, more complex species containing several C and possibly O atoms. Comparisons between the temperature programed desorption (TPD) mass spectra of irradiated and unirradiated films show the electron-induced formation of new chemical species, the identities of which are confirmed by reference to the NIST database of electron impact mass spectra and by TPD measurements of films composed of the proposed products. New species observed in the TPD of irradiated mixture films include C3H6, C2H5OH, and C2H6. Furthermore, X-ray photoelectron spectroscopy of irradiated films confirms the formation of C—O, C=O, and O=C—O— bonds of newly formed molecules. Our experiments support the view that secondary LEEs produced by ionizing radiation drive the chemistry in irradiated ices in space, irrespective of the radiation type.

  10. Synthesis and gas adsorption study of porous metal-organic framework materials (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.

  11. Post-Synthesis Functionalization of Porous Organic Polymers for CO2 Capture

    KAUST Repository

    Al Otaibi, Mona S.


    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

  12. The role of carbon monoxide signaling in the responses of plants to abiotic stresses. (United States)

    He, Huyi; He, Longfei


    Whether carbon monoxide (CO) exerts toxic or protective effect is dependent on the concentration and location of CO in animals. Similarly, it has been increasingly evident that CO also is involved in diverse physiological processes in plants, from seed germination and dormancy to stomatal closure to regulation of multiple environmental stresses. In this review, we focus on CO synthesis and the role of CO in plant responses to abiotic stresses, such as salinity, drought, cadmium and mercury. In general, abiotic stresses induce CO production in plants. CO can alleviate oxidative damage by improving the activities of antioxidative enzymes and antioxidant metabolism. In addition, cross talk between CO signaling and other signaling molecules including nitric oxide (NO) and hydrogen peroxide (H(2)O(2)) also is discussed. Copyright © 2014 Elsevier Inc. All rights reserved.

  13. 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


    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

  14. How does the general public view posthumous organ donation? A meta-synthesis of the qualitative literature. (United States)

    Newton, Joshua D


    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. 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. 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. These findings afford insights into how individuals perceive

  15. Facile synthesis of fluorine-substituted benzothiadiazole-based organic semiconductors and their use in solution-processed small-molecule organic solar cells. (United States)

    Cho, Nara; Song, Kihyung; Lee, Jae Kwan; Ko, Jaejung


    A facile new protocol for the synthesis of iodinated derivatives of fluorinated benzothiadiazoles is demonstrated for the production of p-type semiconducting materials. The newly synthesized small-molecule compounds bis[TPA-diTh]-MonoF-BT and bis[TPA-diTh]-DiF-BT exhibited a power conversion efficiency of 2.95% and a high open-circuit voltage of 0.85 V in solution-processed small-molecule organic solar cells. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Unveiling the Redox Control of Plant Reproductive Development during Abiotic Stress. (United States)

    Zinta, Gaurav; Khan, Asif; AbdElgawad, Hamada; Verma, Vipasha; Srivastava, Ashish Kumar


    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.

  17. Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion (United States)


    The current status of homogeneous iron catalysis in organic chemistry is contemplated, as are the reasons why this particular research area only recently starts challenging the enduring dominance of the late and mostly noble metals over the field. Centered in the middle of the d-block and able to support formal oxidation states ranging from −II to +VI, iron catalysts hold the promise of being able to encompass organic synthesis at large. They are expected to serve reductive as well as oxidative regimes, can emulate “noble tasks”, but are also able to adopt “early” transition metal character. Since a comprehensive coverage of this multidimensional agenda is beyond the scope of an Outlook anyway, emphasis is laid in this article on the analysis of the factors that perhaps allow one to control the multifarious chemical nature of this earth-abundant metal. The challenges are significant, not least at the analytical frontier; their mastery mandates a mindset that differs from the routines that most organic chemists interested in (noble metal) catalysis tend to cultivate. This aspect notwithstanding, it is safe to predict that homogeneous iron catalysis bears the chance to enable a responsible paradigm for chemical synthesis and a sustained catalyst economy, while potentially providing substantial economic advantages. This promise will spur the systematic and in-depth investigations that it takes to upgrade this research area to strategy-level status in organic chemistry and beyond. PMID:27981231

  18. Sol-gel (template) synthesis of macroporous Mo-based catalysts for hydrothermal oxidation of radionuclide-organic complexes (United States)

    Papynov, E. K.; Palamarchuk, M. S.; Mayorov, V. Yu; Modin, E. B.; Portnyagin, A. S.; Sokol'nitskaya, T. A.; Belov, A. A.; Tananaev, I. G.; Avramenko, V. A.


    Molybdenum compounds are industrially demanding as heterogeneous catalysts for oxidation of various organic substances. Highly porous structure of molybdenum-containing catalysts avoids surface's colmatation and prevents blocking catalytic sites that makes these materials play a key role in processes of hydrothermal oxidation of radionuclide organic complexes. The study presents an original way of sol-gel synthesis of new macroporous molybdenum compounds using ;core-shell; colloid template (polymer latex) as poreforming agent. We have described three individual routs of template removal via thermal decomposition to obtain porous materials based on molybdenum compounds. Thermal treatment conditions (temperature, gaseous atmosphere) have been studied with respect to their influence on composition, structure and catalytic properties of synthesized molybdenum systems. The optimal way to synthesis of crystal molybdenum (VI) oxide with ordered porous structure (mean pore size 100-160 nm) has been suggested. Catalytic properties of macroporous molybdenum materials have been investigated in the process of liquid phase and hydrothermal oxidation of such organic substances thiazine and stable Co-EDTA complex. It was shown that macroporous molybdenum oxides could be applied as prospective catalysts for hydrothermal oxidation of organic radionuclide complexes during the processing of radioactive waste.

  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


    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. Bringing the science of proteins into the realm of organic chemistry: total chemical synthesis of SEP (synthetic erythropoiesis protein). (United States)

    Kent, Stephen B H


    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. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. The Potential Role of Formate for Synthesis and Life in Serpentinization Systems (United States)

    Lang, S. Q.; Frueh-Green, G. L.; Bernasconi, S. M.; Brazelton, W. J.; McGonigle, J. M.


    The high hydrogen concentrations produced during water-rock serpentinization reactions provide abundant thermodynamic energy that can drive the synthesis of organic compounds both biotically and abiotically. We investigated the synthesis of abiotic carbon and the metabolic pathways of the microbial inhabitants of the high energy but low diversity serpentinite-hosted Lost City Hydrothermal Field. High concentrations of the organic acid formate can be attributed to two sources. In some locations formate lacks detectable 14C, demonstrating it was formed abiotically from mantle-derived CO2. In other locations there is an additional modern contribution to the formate pool, potentially indicating active cycling with modern seawater dissolved inorganic carbon by microorganisms. The presence of this carbon source is likely critical for the survival of the subsurface microbial communities that inhabit alkaline serpentinization environments, where inorganic carbon is severely limited. Archaeal lipids produced by the Lost City Methanosarcinales (LCMS) also largely lack 14C, requiring their carbon source to be similarly 14C-free. Metagenomic evidence suggests that the LCMS could use formate for methanogenesis and, altogether, the data suggests that these organisms cannot rely on inorganic carbon as their carbon source and substrate for methanogenesis. Considering the lack of dissolved inorganic carbon in this system, the ability to utilize formate may have been a key evolutionary adaptation for survival in serpentinite-hosted environments. In the Lost City system, the LCMS apparently rely upon an abiotically produced organic carbon source, which may enable the Lost City microbial ecosystem to survive in the absence of photosynthesis or its byproducts.

  2. 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


    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.

  3. CsSAD: a fatty acid desaturase gene involved in abiotic resistance in Camellia sinensis (L.). (United States)

    Ding, Z T; Shen, J Z; Pan, L L; Wang, Y U; Li, Y S; Wang, Y; Sun, H W


    Tea (Camellia sinensis L.) is a thermophilic evergreen woody plant that has poor cold tolerance. The SAD gene plays a key role in regulating fatty acid synthesis and membrane lipid fluidity in response to temperature change. In this study, full-length SAD cDNA was cloned from tea leaves using rapid amplification of cDNA ends and polymerase chain reaction (PCR)-based methods. Sequence analysis demonstrated that CsSAD had a high similarity to other corresponding cDNAs. At 25°C, the CsSAD transcriptional level was highest in the leaf and lowest in the stem, but there was no obvious difference between the root and stem organs. CsSAD expression was investigated by reverse transcription-PCR, which showed that CsSAD was upregulated at 4° and -5°C. At 25°C, CsSAD was induced by polyethylene glycol, abscisic acid, and wounding, and a similar trend was observed at 4°C, but the mean expression level at 4°C was lower than that at 25°C. Under natural cold acclimation, the 'CsCr05' variety's CsSAD expression level increased before decreasing. The CsSAD expression level in variety 'CsCr06' showed no obvious change at first, but rapidly increased to a maximum when the temperature was very low. Our study demonstrates that CsSAD is upregulated in response to different abiotic conditions, and that it is important to study the stress resistance of the tea plant, particularly in response to low temperature, drought, and wounding.

  4. Molecular characterization of BZR transcription factor family and abiotic stress induced expression profiling in Brassica rapa. (United States)

    Saha, Gopal; Park, Jong-In; Jung, Hee-Jeong; Ahmed, Nasar Uddin; Kayum, Md Abdul; Kang, Jong-Goo; Nou, Ill-Sup


    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. Copyright © 2015 Elsevier Masson SAS. All rights reserved.

  5. A robust microfluidic device for the synthesis and crystal growth of organometallic polymers with highly organized structures. (United States)

    Liu, Xiao; Yi, Qiaolian; Han, Yongzhen; Liang, Zhenning; Shen, Chaohua; Zhou, Zhengyang; Sun, Jun-Liang; Li, Yizhi; Du, Wenbin; Cao, Rui


    A simple and robust microfluidic device was developed to synthesize organometallic polymers with highly organized structures. The device is compatible with organic solvents. Reactants are loaded into pairs of reservoirs connected by a 15 cm long microchannel prefilled with solvents, thus allowing long-term counter diffusion for self-assembly of organometallic polymers. The process can be monitored, and the resulting crystalline polymers are harvested without damage. The device was used to synthesize three insoluble silver acetylides as single crystals of X-ray diffraction quality. Importantly, for the first time, the single-crystal structure of silver phenylacetylide was determined. The reported approach may have wide applications, such as crystallization of membrane proteins, synthesis and crystal growth of organic, inorganic, and polymeric coordination compounds, whose single crystals cannot be obtained using traditional methods. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Self-assembly versus stepwise synthesis: heterometal-organic frameworks based on metalloligands with tunable luminescence properties. (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


    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. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Colloidal Synthesis of CH3 NH3 PbBr3 Nanoplatelets with Polarized Emission through Self-Organization. (United States)

    Liu, Lige; Huang, Sheng; Pan, Longfei; Shi, Li-Jie; Zou, Bingsuo; Deng, Luogen; Zhong, Haizheng


    We report a combined experimental and theoretical study of the synthesis of CH3 NH3 PbBr3 nanoplatelets through self-organization. Shape transformation from spherical nanodots to square or rectangular nanoplatelets can be achieved by keeping the preformed colloidal nanocrystals at a high concentration (3.5 mg mL-1 ) for 3 days, or combining the synthesis of nanodots with self-organization. The average thickness of the resulting CH3 NH3 PbBr3 nanoplatelets is similar to the size of the original nanoparticles, and we also noticed several nanoplatelets with circular or square holes, suggesting that the shape transformation experienced a self-organization process through dipole-dipole interactions along with a realignment of dipolar vectors. Additionally, the CH3 NH3 PbBr3 nanoplatelets exhibit excellent polarized emissions for stretched CH3 NH3 PbBr3 nanoplatelets embedded in a polymer composite film, showing advantageous photoluminescence properties for display backlights. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Synthesis and Characterization of Metal-Organic Frameworks (MOFs) for Photon Collection and Energy Transfer (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

  9. N-Heterocyclic carbene/Brønsted acid cooperative catalysis as a powerful tool in organic synthesis

    Directory of Open Access Journals (Sweden)

    Rob De Vreese


    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.

  10. 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


    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.

  11. Generation of RNA in abiotic conditions. (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

  12. The synthesis of organic charge transfer hetero-microtubules by crack welding. (United States)

    Kim, J; Chung, J; Hyon, J; Kwon, T; Seo, C; Nam, J; Kang, Y


    The strain-induced cracks in organic microtubules composed of an organic charge transfer (CT) complex of 1,2,4,5-tetracyanobenzene (TCNB) and naphthalene were selectively welded via the formation of secondary CT complexes; this process, in turn, led to the formation of organic hetero-microtubules consisting of multiple segments of two organic CT complexes.

  13. Massive production of abiotic methane during subduction evidenced in metamorphosed ophicarbonates from the Italian Alps. (United States)

    Vitale Brovarone, Alberto; Martinez, Isabelle; Elmaleh, Agnès; Compagnoni, Roberto; Chaduteau, Carine; Ferraris, Cristiano; Esteve, Imène


    Alteration of ultramafic rocks plays a major role in the production of hydrocarbons and organic compounds via abiotic processes on Earth and beyond and contributes to the redistribution of C between solid and fluid reservoirs over geological cycles. Abiotic methanogenesis in ultramafic rocks is well documented at shallow conditions, whereas natural evidence at greater depths is scarce. Here we provide evidence for intense high-pressure abiotic methanogenesis by reduction of subducted ophicarbonates. Protracted (≥0.5-1 Ma), probably episodic infiltration of reduced fluids in the ophicarbonates and methanogenesis occurred from at least ∼40 km depth to ∼15-20 km depth. Textural, petrological and isotopic data indicate that methane reached saturation triggering the precipitation of graphitic C accompanied by dissolution of the precursor antigorite. Continuous infiltration of external reducing fluids caused additional methane production by interaction with the newly formed graphite. Alteration of high-pressure carbonate-bearing ultramafic rocks may represent an important source of abiotic methane, with strong implications for the mobility of deep C reservoirs.

  14. Nanostructured Interfaces for Organized Mesoscopic Biotic-Abiotic Materials (United States)


    silk I and silk II regions retain their intrinsic chemical and mechanical characteristics and show well- developed modulation of localized properties...and the modulation of the substrate signal can be employed for the rapid and non-destructive identification of the crystal growth direction and...styrenesulfonate) (PSS), serve for confining CdTe nanoparticles stabilized by thioglycolic acid, while a poly(methacrylic acid) (PMAA) hydrogel

  15. Use of organic precursors and graphenes in the controlled synthesis of carbon-containing nanomaterials for energy storage and conversion. (United States)

    Yang, Shubin; Bachman, Robert E; Feng, Xinliang; Müllen, Klaus


    The development of high-performance electrochemical energy storage and conversion devices, including supercapacitors, lithium-ion batteries, and fuel cells, is an important step on the road to alternative energy technologies. Carbon-containing nanomaterials (CCNMs), defined here as pure carbon materials and carbon/metal (oxide, hydroxide) hybrids with structural features on the nanometer scale, show potential application in such devices. Because of their pronounced electrochemical activity, high chemical and thermal stability and low cost, researchers are interested in CCNMs to serve as electrodes in energy-related devices. Various all-carbon materials are candidates for electrochemical energy storage and conversion devices. Furthermore, carbon-based hybrid materials, which consist of a carbon component with metal oxide- or metal hydroxide-based nanostructures, offer the opportunity to combine the attractive properties of these two components and tune the behavior of the resulting materials. As such, the design and synthesis of CCNMs provide an attractive route for the construction of high-performance electrode materials. Studies in these areas have revealed that both the composition and the fabrication protocol employed in preparing CCNMs influence the morphology and microstructure of the resulting material and its electrochemical performance. Consequently, researchers have developed several synthesis strategies, including hard-templated, soft-templated, and template-free synthesis of CCNMs. In this Account, we focus on recent advances in the controlled synthesis of such CCNMs and the potential of the resulting materials for energy storage or conversion applications. The Account is divided into four major categories based on the carbon precursor employed in the synthesis: low molecular weight organic or organometallic molecules, hyperbranched or cross-linked polymers consisting of aromatic subunits, self-assembling discotic molecules, and graphenes. In each case

  16. Student-Fabricated Microfluidic Devices as Flow Reactors for Organic and Inorganic Synthesis (United States)

    Feng, Z. Vivian; Edelman, Kate R.; Swanson, Benjamin P.


    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…

  17. Organic template free synthesis of ZSM11 from kaolinite clay | Ajayi ...

    African Journals Online (AJOL)

    Zeolite ZSM11 is a promising catalyst that finds application in area not limited to benzene alkylation, gasoline formation from methanol, conversion of low density polyethene into hydrocarbon, etc. Accordingly, this work present successful synthesis of zeolite ZSM11 from kaolinite clay, seeded with NaY type zeolite and aged ...

  18. A Multistep Synthesis Featuring Classic Carbonyl Chemistry for the Advanced Organic Chemistry Laboratory (United States)

    Duff, David B.; Abbe, Tyler G.; Goess, Brian C.


    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…

  19. A Green, Enantioselective Synthesis of Warfarin for the Undergraduate Organic Laboratory (United States)

    Wong, Terence C.; Sultana, Camille M.; Vosburg, David A.


    The enantioselective synthesis of drugs is of fundamental importance in the pharmaceutical industry. In this experiment, students synthesize either enantiomer of warfarin, a widely used anticoagulant, in a single step from inexpensive starting materials. Stereoselectivity is induced by a commercial organocatalyst, ("R","R")- or…


    Directory of Open Access Journals (Sweden)

    Gushylyk B.


    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

  1. The Synthesis and Methanolysis of Benzyl Tosylates: An Advanced Organic Chemistry Laboratory Experiment. (United States)

    Garst, Michael E.; Gribble, Gordon W.


    Describes a series of experiments (requiring six hours/week for six to eight weeks) involving the synthesis and methanolysis of substituted benzyl tosylates. The experiments provide students with experiences in kinetic data manipulation and an introduction and firm basis for structure-activity relationships and solvent effects in organic…

  2. Enzymatic synthesis of polyol seters in aqueous - organic two-phase systems

    NARCIS (Netherlands)

    Janssen, A.


    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

  3. Declining of forests - biotic and abiotic stress

    Directory of Open Access Journals (Sweden)

    Radulović Zlatan


    Full Text Available During the last several years, a significant decline of different forests in Serbia was recorded. The decline is more widespread in conifer stands, but occurence of decline was recorded in broadleaved forest stands as well. These declines are the result of abiotic, biotic and anthropogenic factors. According to the studies performed so far in Serbia, the predisposing factor were droughts during the 2012 and 2013 vegetation periods that caused physiological weakness of the trees. Among the biotic factors, the most important are fungi (mainly root rot, but rot fungi, and needle diseases and insects (bark beetles in conifer species and defoliators in broadleaved species. [Projekat Ministarstva nauke Republike Srbije, br. TR 37008 i br. TR 31070

  4. Soft templating strategies for the synthesis of mesoporous materials: inorganic, organic-inorganic hybrid and purely organic solids. (United States)

    Pal, Nabanita; Bhaumik, Asim


    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. Copyright © 2012 Elsevier B.V. All rights reserved.

  5. The Role of Micro-Ribonucleic Acids in Legumes with a Focus on Abiotic Stress Response

    Directory of Open Access Journals (Sweden)

    Nitin Mantri


    Full Text Available Legumes are special group of N-fixing plants that are an essential component of cropping system and important source of food and feed for human and animal consumption. Like other crops, the productivity of legumes is threatened by environmental stresses caused due to global climate change. Abiotic stress tolerance is complex trait involving a suite of genes, the expression of which is controlled by transcription factors including gene and/or polypeptide sequences. Recently, micro-ribonucleic acids (miRNAs have been increasingly recognized for their role in regulating the synthesis of polypeptides from different messenger ribonucleic acids (mRNAs including those that act as transcription factors. This review summarizes the current knowledge on the role of different miRNAs in response to main abiotic stresses in legumes. We found consistent as well as conflicting results within and between different legume species. This highlights that we have barely scratched the surface and very comprehensive and targeted experiments will be required in future to underpin the role of miRNAs in controlling the expression of important genes associated with abiotic stress tolerances.

  6. Self-organized Ruthenium-Barium Core-Shell Nanoparticles on a Mesoporous Calcium Amide Matrix for Efficient Low-Temperature Ammonia Synthesis. (United States)

    Kitano, Masaaki; Inoue, Yasunori; Sasase, Masato; Kishida, Kazuhisa; Kobayashi, Yasukazu; Nishiyama, Kohei; Tada, Tomofumi; Kawamura, Shigeki; Yokoyama, Toshiharu; Hara, Michikazu; Hosono, Hideo


    A low-temperature ammonia synthesis process is required for on-site synthesis. Here, we report that barium-doped calcium amide (Ba-Ca(NH2)2) significantly enhances the ammonia synthesis activities of Ru and Co by two-orders of magnitude more than that of a conventional Ru catalyst below 300ºC. Furthermore, the present catalysts are superior to that of the wüstite-based Fe catalyst known as a highly active industrial catalyst at low temperatures and pressures. Nanosized Ru-Ba core-shell structures are self-organized on the support during hydrogen pretreatment, and the support material is simultaneously converted into a mesoporous structure with a high surface area (>100 m2 g-1). These unique self-organized nanostructures account for the high catalytic performance in low-temperature ammonia synthesis. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Advances in genetic engineering for plants abiotic stress control ...

    African Journals Online (AJOL)

    Agricultural productivity is highly influenced by abiotic stresses, known as the most harmful factor concerning the growth and productivity of crops worldwide. Furthermore, industrial crops are nowadays highly influenced by abiotic stress; these include extremes in temperature, drought, salinity, heavy metals and radiation.

  8. Additional insights into the adaptation of cotton plants under abiotic ...

    African Journals Online (AJOL)

    Additional insights into the adaptation of cotton plants under abiotic stresses by in silico analysis of conserved miRNAs in cotton expressed sequence tag database (dbEST) ... Interestingly, miRNAs reported in this study were found to have several targets that are involved in abiotic stress resistance. Considering all together ...

  9. Particle size studies to reveal crystallization mechanisms of the metal organic framework HKUST-1 during sonochemical synthesis. (United States)

    Armstrong, Mitchell R; Senthilnathan, Sethuraman; Balzer, Christopher J; Shan, Bohan; Chen, Liang; Mu, Bin


    Systematic studies of key operating parameters for the sonochemical synthesis of the metal organic framework (MOF) HKUST-1(also called CuBTC) were performed including reaction time, reactor volume, sonication amplitude, sonication tip size, solvent composition, and reactant concentrations analyzed through SEM particle size analysis. Trends in the particle size and size distributions show reproducible control of average particle sizes between 1 and 4μm. These results along with complementary studies in sonofragmentation and temperature control were conducted to compare these results to kinetic crystal growth models found in literature to develop a plausible hypothetical mechanism for ultrasound-assisted growth of metal-organic-frameworks composed of a competitive mechanism including constructive solid-on-solid (SOS) crystal growth and a deconstructive sonofragmentation. Copyright © 2016 Elsevier B.V. All rights reserved.

  10. Bridging the gap between cell biology and organic chemistry: chemical synthesis and biological application of lipidated peptides and proteins. (United States)

    Peters, Carsten; Wagner, Melanie; Völkert, Martin; Waldmann, Herbert


    We have developed a basic concept for studying cell biological phenomena using an interdisciplinary approach starting from organic chemistry. Based on structural information available for a given biological phenomenon, unsolved chemical problems are identified. For their solution, new synthetic pathways and methods are developed, which reflect the state of the art in synthesising lipidated peptide conjugates. These compounds are used as molecular probes for the investigation of biological phenomena that involve both the determination of biophysical properties and cell biological studies. The interplay between organic synthesis, biophysics and cell biology in the study of protein lipidation may open up new and alternative opportunities to gain knowledge about the biological phenomenon that could not be obtained by employing biological techniques alone. This fruitful combination is highlighted using the Ras protein as an outstanding example. Included herein is: the development of methods for the synthesis of Ras-derived peptides and fully functional Ras proteins, the determination of the biophysical properties, in particular the ability to bind to model membranes, and finally the use of synthetic Ras peptides and proteins in cell biological experiments.

  11. Enzymatic synthesis of polyol seters in aqueous - organic two-phase systems


    A. Janssen


    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. These esters consist of a nonpolar part (fatty acid) and a polar part (polyol). Therefore, polyol esters have surface-active properties and are used as emulsifier in food, pharmaceutics; an...

  12. Modulated synthesis of chromium-based metal-organic framework (MIL-101) with enhanced hydrogen uptake

    CSIR Research Space (South Africa)

    Ren, Jianwei


    Full Text Available -1 International Journal of Hydrogen Energy Vol. 39(23) Modulated synthesis of chromium-based metalorganic framework (MIL-101) with enhanced hydrogen uptake Jianwei Ren a,*, Nicholas M. Musyoka a, Henrietta W. Langmi a, Tshiamo Segakweng a, Brian C. North... a, Mkhulu Mathe a, Xiangdong Kang b a HySA Infrastructure Centre of Competence, Materials Science and Manufacturing, Council for Scientific and Industrial Research (CSIR), PO Box 395, Pretoria 0001, South Africa b Shenyang National Laboratory...

  13. Synthesis and morphogenesis of organic and inorganic polymers by means of biominerals and biomimetic materials. (United States)

    Kijima, Misako; Oaki, Yuya; Munekawa, Yurika; Imai, Hiroaki


    We have studied the simultaneous synthesis and morphogenesis of polymer materials with hierarchical structures from nanoscopic to macroscopic scales. The morphologies of the original materials can be replicated to the polymer materials. In general, it is not easy to achieve the simultaneous synthesis and morphogenesis of polymer material even using host materials. In the present work, four biominerals and three biomimetic mesocrystal structures are used as the host materials or templates and polypyrrole, poly(3-hexylthiopehene), and silica were used as the precursors for the simultaneous syntheses and morphogenesis of polymer materials. The host materials with the hierarchical structure possess the nanospace for the incorporation of the monomers. After the incorporation of the monomers, the polymerization reaction proceeds in the nanospace with addition of the initiator agents. Then, the dissolution of the host materials leads to the formation and morphogenesis of the polymer materials. The scheme of the replication can be classified into the three types based on the structures of the host materials (types I-III). The type I template facilitates the hierarchical replication of the whole host material, type II mediates the hierarchical surface replication, and type III induces the formation of the two-dimensional nanosheets. Based on these results, the approach for the coupled synthesis and morphogenesis can be applied to a variety of combinations of the templates and polymer materials. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. MicroRNAs As Potential Targets for Abiotic Stress Tolerance in Plants (United States)

    Shriram, Varsha; Kumar, Vinay; Devarumath, Rachayya M.; Khare, Tushar S.; Wani, Shabir H.


    The microRNAs (miRNAs) are small (20–24 nt) sized, non-coding, single stranded riboregulator RNAs abundant in higher organisms. Recent findings have established that plants assign miRNAs as critical post-transcriptional regulators of gene expression in sequence-specific manner to respond to numerous abiotic stresses they face during their growth cycle. These small RNAs regulate gene expression via translational inhibition. Usually, stress induced miRNAs downregulate their target mRNAs, whereas, their downregulation leads to accumulation and function of positive regulators. In the past decade, investigations were mainly aimed to identify plant miRNAs, responsive to individual or multiple environmental factors, profiling their expression patterns and recognizing their roles in stress responses and tolerance. Altered expressions of miRNAs implicated in plant growth and development have been reported in several plant species subjected to abiotic stress conditions such as drought, salinity, extreme temperatures, nutrient deprivation, and heavy metals. These findings indicate that miRNAs may hold the key as potential targets for genetic manipulations to engineer abiotic stress tolerance in crop plants. This review is aimed to provide recent updates on plant miRNAs, their biogenesis and functions, target prediction and identification, computational tools and databases available for plant miRNAs, and their roles in abiotic stress-responses and adaptive mechanisms in major crop plants. Besides, the recent case studies for overexpressing the selected miRNAs for miRNA-mediated enhanced abiotic stress tolerance of transgenic plants have been discussed. PMID:27379117

  15. Synthesis and characterization of silicon-based polymers for use as organic/inorganic hybrids and silicon carbide precursors (United States)

    Sellinger, Alan

    Organic/inorganic hybrids from silsesquioxanes. This Dissertation describes the synthesis and characterization of methacrylate, epoxy and liquid crystalline (LC)-containing organic/inorganic hybrid materials based on silsesquioxanes. While the methacrylate and epoxy groups provide polymerizable moieties to the hybrids, the LC component is anticipated to provide toughness, and oxidative stability as well as minimize shrinkage during curing. The inorganic silsesquioxane portion, ((RSiOsb{1.5})sb8, cubes), which closely resembles specific crystalline forms of silica and zeolites, may be covalently linked to a variety of organic functional groups. As a result, single-phase organic/inorganic hybrids are formed that when polymerized mimic silica-reinforced composites. The resultant hybrids are liquids at room temperature, and hence allow for single-phase composite processing, ideal for abrasion-resistant coatings and filling molds, as in dental restorative applications. The reactions are based on inexpensive starting materials, have high yields (>80%), and form soluble products containing up to 65% masked silica. The hybrids were characterized using NMR spectroscopy (sp1H,\\ sp{13}C,\\ sp{29}Si), FTIR, size exclusion chromatography (SEC), and thermal analysis (TGA, DSC). A modified polymethylsilane as a precursor of silicon carbide. It is generally known that polymer precursor routes to silicon carbide (SiC) are very important in the processing of SiC fibers and high performance SiC parts with specific shapes. It is further known that commercial SiC precursor polymers are often not resistant to oxidation, and are based on monomers rich in carbon. As a result of this, their pyrolysis yields SiC rich in oxygen and carbon, a feature which drastically reduces the final materials' ultimate properties (high temperature resistance, tensile strength, modulus). To remedy this, we describe in this work the synthesis and characterization of a modified polymethylsilane (mPMS) which

  16. De novo synthesis of a metal-organic framework material featuring ultrahigh surface area and gas storage capacities. (United States)

    Farha, Omar K; Yazaydın, A Özgür; Eryazici, Ibrahim; Malliakas, Christos D; Hauser, Brad G; Kanatzidis, Mercouri G; Nguyen, SonBinh T; Snurr, Randall Q; Hupp, Joseph T


    Metal-organic frameworks--a class of porous hybrid materials built from metal ions and organic bridges--have recently shown great promise for a wide variety of applications. The large choice of building blocks means that the structures and pore characteristics of the metal-organic frameworks can be tuned relatively easily. However, despite much research, it remains challenging to prepare frameworks specifically tailored for particular applications. Here, we have used computational modelling to design and predictively characterize a metal-organic framework (NU-100) with a particularly high surface area. Subsequent experimental synthesis yielded a material, matching the calculated structure, with a high BET surface area (6,143 m(2) g(-1)). Furthermore, sorption measurements revealed that the material had high storage capacities for hydrogen (164 mg g(-1)) and carbon dioxide (2,315 mg g(-1))--gases of high importance in the contexts of clean energy and climate alteration, respectively--in excellent agreement with predictions from modelling.

  17. Synthesis of magnetic nanoporous carbon from metal-organic framework for the fast removal of organic dye from aqueous solution

    Energy Technology Data Exchange (ETDEWEB)

    Jiao, Caina; Wang, Yanen; Li, Menghua; Wu, Qiuhua; Wang, Chun; Wang, Zhi, E-mail:


    In this paper, a magnetic nanoporous carbon (Fe{sub 3}O{sub 4}/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 N{sub 2} adsorption–desorption isotherms. The Fe{sub 3}O{sub 4}/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 Fe{sub 3}O{sub 4}/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 Fe{sub 3}O{sub 4}/NPC can be used as a good alternative for the effective removal of organic dyes from wastewater. - Highlights: • Fe{sub 3}O{sub 4}/NPC nanocomposite was synthesized by choosing MOF-5 as carbon precursor. • Fe{sub 3}O{sub 4}/NPC was used as an adsorbent for removal of organic dye from aqueous solution. • Fe{sub 3}O{sub 4}/NPC could be a promising candidate for pollutants removal.

  18. Controlled Synthesis of Organic/Inorganic van der Waals Solid for Tunable Light-Matter Interactions. (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


    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. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Gene expression and content of enzymes of noradrenaline synthesis in the rat organ of Zuckerkandl at the critical period of morphogenesis. (United States)

    Murtazina, A R; Nikishina, Yu O; Bondarenko, N S; Sapronova, A Ya; Volina, E V; Ugrumov, M V


    Gene expression and content of the key enzymes involved in the synthesis of noradrenaline-tyrosine hydroxylase and dopamine beta-hydroxylase-was evaluated in the organ of Zuckerkandl of rats in the critical period of morphogenesis. High levels of mRNA and protein of both enzymes in the perinatal period of development and their sharp decline on day 30 of postnatal development were detected. These data indicate that the synthesis of noradrenaline in the organ of Zuckerkandl is maximum during the critical period of morphogenesis and decreases during the involution of this paraganglion.

  20. Atmospheric Prebiotic Chemistry and Organic Hazes (United States)

    Trainer, Melissa G.


    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.

  1. Organic synthesis and inhibition action of novel hydrazide derivative for mild steel corrosion in acid solutions

    Energy Technology Data Exchange (ETDEWEB)

    Abdallah, Zeinab A. [Department of Chemistry, Faculty of Science, Cairo University, Giza (Egypt); Mohamed Ahmed, Mohamed S., E-mail: [Department of Chemistry, Faculty of Science, Cairo University, Giza (Egypt); Saleh, M.M., E-mail: [Department of Chemistry, Faculty of Science, Cairo University, Giza (Egypt); Chemistry Department, College of Science, King Faisal University, Al-Hassa (Saudi Arabia)


    A new derivative of hydrazide family, 2-(2-hydrazinyl-1,6-dihydro-6-oxopyrimidin-4-yl) acetohydrazide (HDOP) is synthesized and used as a corrosion inhibitor for mild steel both in 1 M HCl and 0.5 M H{sub 2}SO{sub 4} solutions. A facial synthesis of a novel hydrazinyl hydrazide derivative is accomplished via a one-pot synthesis. Reaction of ethyl 2-(1,2,3,6-tetrahydro-6-oxo-2-thiopyrimidin-4-yl)acetate (1) with hydrazine hydrate in an ethanol refluxing produces the target hydrazinyl hydrazide derivative in a good yield. Different techniques such as IR, NMR and mass spectroscopy are used for characterization of the obtained products. The inhibition of mild steel corrosion using HDOP in different concentrations is studied by electrochemical impedance spectroscopy and polarization measurements. The inhibition efficiency (IE) of HDOP is found to be higher in HCl than that in H{sub 2}SO{sub 4} solution. This is attributed to the stronger adsorption of Cl{sup −} on the iron surface which enables better synergism between Cl{sup −} and the protonated inhibitor. The HDOP acts mainly as a cathodic inhibitor (in both acid solutions) and an inhibition efficiency of ∼89% was obtained in the HCl solution. The free energy of adsorption obtained by applying Langmuir adsorption isotherm predicts physisorption of HDOP on the iron surface in the HCl solution. - Highlights: • One-pot synthesis of novel hydrazinyl hydrazide (HDOP) derivative is described. • Both spectral and elemental analyses are used for characterization of the HDOP. • EIS, Tafel plots, SEM and EDX are used in the corrosion study in HCl and H{sub 2}SO{sub 4}.

  2. Electrochemical Synthesis of a Microporous Conductive Polymer Based on a Metal-Organic Framework Thin Film

    KAUST Repository

    Lu, Chunjing


    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. Structural organization of films based on polyaniline/polysulfonic acid complexes depending on the synthesis method

    Energy Technology Data Exchange (ETDEWEB)

    Simagina, L. V., E-mail:; Gaynutdinov, R. V.; Stepina, N. D.; Sorokina, K. L. [Russian Academy of Sciences, Shubnikov Institute of Crystallography (Russian Federation); Morozova, O. V.; Shumakovich, G. P.; Yaropolov, A. I., E-mail: [Russian Academy of Sciences, Bach Institute of Biochemistry (Russian Federation); Tolstikhina, A. L. [Russian Academy of Sciences, Shubnikov Institute of Crystallography (Russian Federation)


    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.

  4. Brassinosteroid Action in Plant Abiotic Stress Tolerance. (United States)

    Krishna, Priti; Prasad, Bishun D; Rahman, Tawhidur


    Brassinosteroids (BRs) are a class of plant steroidal hormones that play essential roles in plant growth and development. Systematic studies had first been undertaken concomitantly to determine both the effects of exogenous BR on stress phenotypes of Arabidopsis thaliana and Brassica napus (rapeseed) seedlings and the expression of stress marker genes in BR-treated and untreated seedlings. When reproducible and convincing evidence of the role of BR in stress tolerance had been obtained, molecular mechanisms underlying the ability of BR to confer tolerance against heat, cold, drought, and salt stress, as well as pathogen resistance were studied with several molecular approaches and tools. The results of these studies have together provided valuable insights into how BRs, through their control of many basic cellular processes and stress responses, promote vigor in plants and prepare the plant to mount a dynamic response upon environmental challenges. Protocols to assess BR effects on abiotic stress tolerance in Arabidopsis and rapeseed seedlings are described here and they can be fine-tuned and adapted for other plant species.

  5. Synthesis, Processing, and Characterization of Inorganic-Organic Hybrid Cross-Linked Silica, Organic Polyimide, and Inorganic Aluminosilicate Aerogels (United States)

    Nguyen, Baochau N.; Guo, Haiquan N.; McCorkle, Linda S.


    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.

  6. Biomass allocation and C-N-P stoichiometry in C3 and C4 crops under abiotic stress (United States)

    Biomass allocation to structural, metabolic and reproductive organs as well as their carbon, nitrogen and phosphorus (C-N-P) profiles and ratios (C:N, C:P, and N:P) were estimated in C3 and C4 crop plants subjected to multiple abiotic stresses (i.e., combination of temperature and water stress level...

  7. Organic-free synthesis of layer-like FAU-type zeolites. (United States)

    Inayat, A; Schneider, C; Schwieger, W


    The formation of layer-like FAU-type zeolites was facilitated in the absence of any organic template. Instead, the addition of simple inorganic salts turned out to be an effective and easy to handle alternative to organic additives to induce morphological and even structural changes during zeolite crystallisation.

  8. Organic Materials in the Undergraduate Laboratory: Microscale Synthesis and Investigation of a Donor-Acceptor Molecule (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


    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. Chemical Priming of Plants Against Multiple Abiotic Stresses: Mission Possible?

    KAUST Repository

    Savvides, Andreas


    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.

  10. Depletion of abiotic resources in the steel production in Poland

    Directory of Open Access Journals (Sweden)

    D. Burchart-Korol


    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.

  11. Chemical Priming of Plants Against Multiple Abiotic Stresses: Mission Possible? (United States)

    Savvides, Andreas; Ali, Shawkat; Tester, Mark; Fotopoulos, Vasileios


    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. Copyright © 2015 Elsevier Ltd. All rights reserved.

  12. Recent Molecular Advances on Downstream Plant Responses to Abiotic Stress

    Directory of Open Access Journals (Sweden)

    Cláudia Regina Batista de Souza


    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.

  13. Green synthesis of silver nanoparticles by microorganism using organic pollutant: its antimicrobial and catalytic application. (United States)

    Otari, S V; Patil, R M; Nadaf, N H; Ghosh, S J; Pawar, S H


    A novel approach for the green synthesis of silver nanoparticles (AgNPs) from aqueous solution of AgNO3 using culture supernatant of phenol degraded broth is reported in this work. The synthesis was observed within 10 h, and AgNPs showed characteristic surface plasmon resonance around 410 nm. Spherical nanoparticles of size less than 30 nm were observed in transmission electron microscopy. X-ray diffraction pattern corresponding to 111, 200, 220, and 311 revealed the crystalline nature of the as-formed nanoparticles. It was found that the colloidal solution of AgNP suspensions exhibited excellent stability over a wide range of ionic strength, pH, and temperature. The effect of pH and ionic strength indicated that stabilization is due to electrostatic repulsion arising from the negative charge of the conjugate proteins. The AgNPs showed highly potent antimicrobial activity against Gram-positive, Gram-negative, and fungal microorganisms. The as-prepared AgNPs showed excellent catalytic activity in reduction of 4-nitrophenol to 4-aminophenol by NaBH4. By manufacturing magnetic alginate beads, the reusability of the AgNPs for the catalytic reaction has been demonstrated.

  14. Synthesis, Isotopic Enrichment, and Solid-State NMR Characterization of Zeolites Derived from the Assembly, Disassembly, Organization, Reassembly Process. (United States)

    Bignami, Giulia P M; Dawson, Daniel M; Seymour, Valerie R; Wheatley, Paul S; Morris, Russell E; Ashbrook, Sharon E


    The great utility and importance of zeolites in fields as diverse as industrial catalysis and medicine has driven considerable interest in the ability to target new framework types with novel properties and applications. The recently introduced and unconventional assembly, disassembly, organization, reassembly (ADOR) method represents one exciting new approach to obtain solids with targeted structures by selectively disassembling preprepared hydrolytically unstable frameworks and then reassembling the resulting products to form materials with new topologies. However, the hydrolytic mechanisms underlying such a powerful synthetic method are not understood in detail, requiring further investigation of the kinetic behavior and the outcome of reactions under differing conditions. In this work, we report the optimized ADOR synthesis, and subsequent solid-state characterization, of (17)O- and doubly (17)O- and (29)Si-enriched UTL-derived zeolites, by synthesis of (29)Si-enriched starting Ge-UTL frameworks and incorporation of (17)O from (17)O-enriched water during hydrolysis. (17)O and (29)Si NMR experiments are able to demonstrate that the hydrolysis and rearrangement process occurs over a much longer time scale than seen by diffraction. The observation of unexpectedly high levels of (17)O in the bulk zeolitic layers, rather than being confined only to the interlayer spacing, reveals a much more extensive hydrolytic rearrangement than previously thought. This work sheds new light on the role played by water in the ADOR process and provides insight into the detailed mechanism of the structural changes involved.

  15. 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


    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.

  16. Synthesis and Electrospraying of Nanoscale MOF (Metal Organic Framework) for High-Performance CO2Adsorption Membrane. (United States)

    Wahiduzzaman; Allmond, Kelsey; Stone, John; Harp, Spencer; Mujibur, Khan


    We report the sonochemical synthesis of MOF (metal organic framework) nanoparticles of 30-200 nm in size and electrospraying of those particles on electrospun nanofibers to process a MOF-attached nanofibrous membrane. This membrane displayed significant selectivity towards CO 2 and capacity of adsorbing with 4000-5000 ppm difference from a mixed gas flow of 1% CO 2 and 99% N 2 . Applying ultrasonic waves during the MOF synthesis offered rapid dispersion and formation of crystalline MOF nanoparticles in room temperature. The MOF nanoparticles of 100-200 nm in size displayed higher surface area and adsorption capacity comparing to that of 30-60 nm in size. Nanofibrous membrane was produced by electrospinning of MOF blended PAN solution followed by electrospraying of additional MOF nanoparticles. This yielded uniform MOF deposition on nanofibers, occurred due to electrostatic attraction between highly charged nanoparticles and conductive nanofibers. A test bench for real-time CO 2 adsorption at room temperature was built with non-dispersive Infrared (NDIR) CO 2 sensors. Comparative tests were performed on the membrane to investigate its enhanced adsorption capacity. Three layers of the as-produced membranes displayed CO 2 adsorption for approximately 2 h. Thermogravimetric analysis (TGA) of the membrane showed the thermal stability of the MOF and PAN up to 290 and 425 °C, respectively.

  17. Synthesis, growth and characterization of organic nonlinear optical material: N-benzyl-2-methyl-4-nitroaniline (BNA) (United States)

    Kalaivanan, R.; Srinivasan, K.


    Synthesis of the organic nonlinear optical compound N-benzyl-2-methyl-4-nitroaniline (BNA) was carried out in a newer chemical environment using the mixture of benzyl chloride and 2-methl-4-nitroaniline by a preferred laboratory synthesis process. The synthesized BNA compound was separated by column chromatography (CC) with low pressure silica gell using petrollium benzine and purity of the separated resultant product was confirmed by thin layer chromatography (TLC). Further, the material was recrystallized atleast four times in methanol and the highly purified BNA was used for the growth of single crystals from solutions with selected solvents by slow evaporation method at room temperature. Single crystals having natural growth morphology were harvested and their different growth faces were identified by optical goniometry. The grown crystals were subjected to different characterization techniques such as powder x-ray diffraction (PXRD), fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC) and UV-vis-Near IR spectroscopy. Further, the second harmonic generation (SHG) efficiency of the grown BNA crystal was studied by Kurtz and Perry powder technique using Nd:YAG laser as fundamental source and found to be twice that of inorganic standard KDP.

  18. The Role of the Relationship between Hydrogen Peroxide and Nitric Oxide in Plant Tolerance to Abiotic Stresses




    Hydrogen peroxide (H2O2)and Nitric oxide (NO) are signalling molecules that play an important role in different organisms. Even though intensive research in the past two decades, knowledge about the role of these two molecules interact with each other in abiotic stress tolerance and the relationship with biological processes aren’t completely elucidated yet. In this paper, H2O2 and NO cross-talk and possible role in plant responses to abiotic stresses such as drought, salinity, extreme temper...

  19. Ultrasound-assisted synthesis of nano-structured Zinc(II)-based metal-organic frameworks as precursors for the synthesis of ZnO nano-structures. (United States)

    Bigdeli, Fahime; Ghasempour, Hosein; Azhdari Tehrani, Alireza; Morsali, Ali; Hosseini-Monfared, Hassan


    A 3D, porous Zn(II)-based metal-organic framework {[Zn 2 (oba) 2 (4-bpmn)]·(DMF) 1.5 } n (TMU-21), (4-bpmn=N,N'-Bis-pyridin-4-ylmethylene-naphtalene-1,5-diamine, H 2 oba=4,4'-oxybis(benzoic acid)) with nano-rods morphology under ultrasonic irradiation at ambient temperature and atmospheric pressure was prepared and characterized by scanning electron microscopy. Sonication time and concentration of initial reagents effects on the size and morphology of nano-structured MOFs were studied. Also {[Zn 2 (oba) 2 (4-bpmn)] (TMU-21) and {[Zn 2 (oba) 2 (4-bpmb)] (TMU-6), 4-bpmb=N,N'-(1,4-phenylene)bis(1-(pyridin-4-yl)methanimine) were easily prepared by mechanochemical synthesis. Nanostructures of Zinc(II) oxide were obtained by calcination of these compounds and their de-solvated analogue as activated MOFs, at 550°C under air atmosphere. As a result of that, different Nanostructures of Zinc(II) oxide were obtained. The ZnO nanoparticles were characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM) and FT-IR spectroscopy. Copyright © 2016 Elsevier B.V. All rights reserved.

  20. Relationships Between Plankton Primary Productivity, Biotic and Abiotic Variables of Carp Fish Ponds

    Directory of Open Access Journals (Sweden)

    Doychin I. Terziyski


    Full Text Available Experiments measuring primary productivity, biotic and abiotic environmental factors in carp ponds were carried out within three consecutive years (2004, 2005 and 2006. The aim of the study was investigation of the relations between the biotic and abiotic variables, their influence on the primary productivity and the effect of manuring on the fish ponds. The influence of environmental factors onto primary productivity was investigated in ponds with and without organic manure. Nitrate nitrogen demonstrated the closest relationship with the gross primary productivity followed by chlorophyll a level and N/P ratio in manured ponds. When no manuring was applied, the importance of the nutrients along the food chain: nutrients– phytoplankton – zooplankton decreased. Trends, which can be used for increasing of productivity in carp ponds, were obtained. They give indications to improve the existing practices for better management of production efficiency and water quality in fish farms.

  1. Controllable Synthesis of Organic Microcrystals with Tunable Emission Color and Morphology Based on Molecular Packing Mode. (United States)

    Li, Zhi-Zhou; Liao, Liang-Sheng; Wang, Xue-Dong


    Organic microcrystals are of essential importance for high fluorescence efficiency, ordered molecular packing mode, minimized defects, and smooth shapes, which are extensively applied in organic optoelectronics. The molecular packing mode significantly influences the optical/electrical properties of organic microcrystals, which makes the controllable preparation of organic microcrystals with desired molecular packing mode extremely important. In the study, yellow-emissive α phase organic microcrystals with rectangular morphology and green-emissive β phase perylene microcrystals with rhombic morphology are separately prepared by simply controlling the solution concentration. The distinct molecular staking modes of the H/J-aggregate are found in these two types of perylene microcrystals, which contribute to the different emission color, morphology, and radiative decay rate. What is more interesting, the α-doped β phase and the β-doped α phase organic microcrystals can also be fabricated by modulating the evaporation rate from 100 to 10 µL min-1 . The findings can contribute to the future development of organic optoelectronics at the microscale. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Synthesis and characterization of a helicene-based imidazolium salt and its application in organic molecular electronics. (United States)

    Storch, Jan; Zadny, Jaroslav; Strasak, Tomas; Kubala, Martin; Sykora, Jan; Dusek, Michal; Cirkva, Vladimir; Matejka, Pavel; Krbal, Milos; Vacek, Jan


    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. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Synthesis of an extra-large molecular sieve using proton sponges as organic structure-directing agents. (United States)

    Martínez-Franco, Raquel; Moliner, Manuel; Yun, Yifeng; Sun, Junliang; Wan, Wei; Zou, Xiaodong; Corma, Avelino


    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.

  4. Synthesis of a conjugated pyrrolopyridazinedione–benzodithiophene (PPD–BDT) copolymer and its application in organic and hybrid solar cells

    KAUST Repository

    Knall, Astrid-Caroline


    Herein, we describe the synthesis and characterization of a conjugated donor–acceptor copolymer consisting of a pyrrolopyridazinedione (PPD) acceptor unit, and a benzodithiophene (BDT) donor unit. The polymerization was done via a Stille cross-coupling polycondensation. The resulting PPD–BDT copolymer revealed an optical bandgap of 1.8 eV and good processability from chlorobenzene solutions. In an organic solar cell in combination with PC70BM, the polymer led to a power conversion efficiency of 4.5%. Moreover, the performance of the copolymer was evaluated in polymer/nanocrystal hybrid solar cells using non-toxic CuInS2 nanocrystals as inorganic phase, which were prepared from precursors directly in the polymer matrix without using additional capping ligands. The PPD–BDT/CuInS2 hybrid solar cells showed comparably high photovoltages and a power conversion efficiency of 2.2%.Graphical abstract

  5. Hollow metal-organic framework nanospheres via emulsion-based interfacial synthesis and their application in size-selective catalysis. (United States)

    Yang, Yufen; Wang, Fengwei; Yang, Qihao; Hu, Yingli; Yan, Huan; Chen, Yu-Zhen; Liu, Huarong; Zhang, Guoqing; Lu, Junling; Jiang, Hai-Long; Xu, Hangxun


    Metal-organic frameworks (MOFs) represent an emerging class of crystalline materials with well-defined pore structures and hold great potentials in a wide range of important applications. The functionality of MOFs can be further extended by integration with other functional materials, e.g., encapsulating metal nanoparticles, to form hybrid materials with novel properties. In spite of various synthetic approaches that have been developed recently, a facile method to prepare hierarchical hollow MOF nanostructures still remains a challenge. Here we describe a facile emulsion-based interfacial reaction method for the large-scale synthesis of hollow zeolitic imidazolate framework 8 (ZIF-8) nanospheres with controllable shell thickness. We further demonstrate that functional metal nanoparticles such as Pd nanocubes can be encapsulated during the emulsification process and used for heterogeneous catalysis. The inherently porous structure of ZIF-8 shells enables encapsulated catalysts to show size-selective hydrogenation reactions.

  6. 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


    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.

  7. Bringing research into a first semester organic chemistry laboratory with the multistep synthesis of carbohydrate-based HIV inhibitor mimics. (United States)

    Pontrello, Jason K


    Benefits of incorporating research experiences into laboratory courses have been well documented, yet examples of research projects designed for the first semester introductory organic chemistry lab course are extremely rare. To address this deficiency, a Carbohydrate-Based human immunodeficiency virus (HIV) Inhibitor project consisting of a synthetic scheme of four reactions was developed for and implemented in the first semester organic lab. Students carried out the synthetic reactions during the last 6 of 10 total labs in the course, generating carbohydrate-based dimeric target molecules modeled after published dimers with application in HIV therapy. The project was designed to provide a research experience through use of literature procedures for reactions performed, exploration of variation in linker length in the target structure, and synthesis of compounds not previously reported in the scientific literature. Project assessment revealed strong student support, indicating enhanced engagement and interest in the course as a direct result of the use of scientific literature and the applications of the synthesized carbohydrate-based molecules. Regardless of discussed challenges in designing a research project for the first semester lab course, the finding from data analysis that a project implemented in the first semester lab had significantly greater student impact than a second semester project should provide motivation for development of additional research projects for a first semester organic course. © 2015 The International Union of Biochemistry and Molecular Biology.

  8. Highly stable new organic-inorganic perovskite (CH₃NH₃)₂PdBr₄: synthesis, structure and physical properties. (United States)

    Liu, Xixia; Huang, Tang Jiao; Zhang, Liuyang; Tang, Baoshan; Zhang, Nengduo; Shi, Diwen; Gong, Hao


    Lead halide perovskite has attracted striking attention recently due to their appealing properties. However, toxicity and stability are two main factors restricting its application. In this work, we experimentally synthesized less toxic and highly stable Pd-based hybrid perovskite after exploring different experimental conditions. This new hybrid organic-inorganic perovskite (CH₃NH₃)₂PdBr₄ was found to be an orthorhombic crystal (Cmce, Z=4) with lattice parameters a=8.00 Å, b=7.99 Å, c= 18.89 Å. The Cmce symmetry and lattices parameters were confirmed using Pawley refinement. The atoms positions were testified based on DFT calculation. This perovskite compound was determined to be a p-type semiconductor, with a resistivity of 102.9 kΩ*cm, a carrier concentration of 3.4 ×1012 /cm³ and a mobility of 23.4 cm² /(V*S). Interestingly, XRD and UV-vis measurements indicated that the phase of this new perovskite was maintained with an optical gap of 1.91 eV after leaving in air with a high humidity of 60% for 4 days, and unchanged for months in N₂ ambiance, much more stable than most existing organic-inorganic perovskites. The synthesis and various characterizations of this work further the understanding of this (CH₃NH₃)₂PdBr₄ organic-inorganic hybrid perovskite material. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Template-mediated Synthesis of Hollow Microporous Organic Nanorods with Tunable Aspect Ratio (United States)

    Li, Qingyin; Jin, Shangbin; Tan, Bien


    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. PMID:27506370

  10. 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)


    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.



    Prapti Rahayu; Witri Wahyu Lestari


    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 ...

  12. Synthesis and Characterization of Surface Mounted Chiral Metal-Organic Frameworks


    Gu, Zhi-Gang


    Chiral surface mounted metal-organic frameworks (SURMOFs), composed of metal ions and chiral organic ligands, have been grown on functionalized substrates and studied in this thesis. On one hand, the impact of the pore size of the chiral SURMOF on the enantioselectivity has been investigated in this thesis. On the other hand, oriented circular dichroism (OCD) was chosen as a tool to investigate the chirality and enantioselective separation property of chiral SURMOFs.

  13. Nucleotide Selectivity in Abiotic RNA Polymerization Reactions (United States)

    Coari, Kristin M.; Martin, Rebecca C.; Jain, Kopal; McGown, Linda B.


    In order to establish an RNA world on early Earth, the nucleotides must form polymers through chemical rather than biochemical reactions. The polymerization products must be long enough to perform catalytic functions, including self-replication, and to preserve genetic information. These functions depend not only on the length of the polymers, but also on their sequences. To date, studies of abiotic RNA polymerization generally have focused on routes to polymerization of a single nucleotide and lengths of the homopolymer products. Less work has been done the selectivity of the reaction toward incorporation of some nucleotides over others in nucleotide mixtures. Such information is an essential step toward understanding the chemical evolution of RNA. To address this question, in the present work RNA polymerization reactions were performed in the presence of montmorillonite clay catalyst. The nucleotides included the monophosphates of adenosine, cytosine, guanosine, uridine and inosine. Experiments included reactions of mixtures of an imidazole-activated nucleotide (ImpX) with one or more unactivated nucleotides (XMP), of two or more ImpX, and of XMP that were activated in situ in the polymerization reaction itself. The reaction products were analyzed using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) to identify the lengths and nucleotide compositions of the polymerization products. The results show that the extent of polymerization, the degree of heteropolymerization vs. homopolymerization, and the composition of the polymeric products all vary among the different nucleotides and depend upon which nucleotides and how many different nucleotides are present in the mixture.

  14. The Future of Organization Design: An Interpretative Synthesis in Three Themes

    Directory of Open Access Journals (Sweden)

    Richard M. Burton


    Full Text Available In the inaugural issue of the Journal of Organization Design (Vol. 1, #1, 2012, noted scholars and experienced practitioners presented their views on the future of organization design. The seven wise and provocative statements were subsequently discussed by members of the Organizational Design Community at a conference held at Harvard University on August 3, 2012. I was asked by JOD to monitor the discussion and identify the broad organization design themes that emerged. Although the discussion was wide ranging, three themes were noticeable. The first theme is that there are fundamentals of organization design, and all agreed that design involves creating a cohesive socio-technical system from a number of constituent elements. The second theme is that the boundaries of many newer organizational forms extend beyond that of the single firm, so the scope of organization design needs to expand to include ecosystems, collaborative communities, industries, and other supra-firm architectures. The third theme involves time and change, requiring a shift in focus from how organizations become stable and predictable to how they can become more agile.

  15. Synthesis and Evaluation of Porous Semiconductor Hexaniobate Nanotubes for Photolysis of Organic Dyes in Wastewater

    Directory of Open Access Journals (Sweden)

    Maryam Zarei-Chaleshtori


    Full Text Available We present the chemical synthesis of hexaniobate nanotubes using two routes, (1 starting material K4Nb6O17 and (2 parent material of H4Nb6O17 via ion exchange. The as-synthesized materials were exfoliated by adjusting the pH to 9–10 using tetra-n-butylammonioum hydroxide (TBA+OH−, leading to a formation of hexaniobate nanotubes. In order to understand morphology a full characterization was conducted using SEM, HRTEM, BET and powder-XRD. The photocatalytic activity was evaluated using photolysis method using Bromocresol Green (BG and Methyl Orange (MO as model contaminants. Results indicate a nanotube porous oxide with large porous and surface area; the photocatalytic activity is about 95% efficient when comparing with commercial TiO2.

  16. Synthesis and Identification of the Organic Reagent Ereochrom Black T and its Complex with Cobalt (lll

    Directory of Open Access Journals (Sweden)

    Jassem M. Abd Al Hassein


    Full Text Available The ligand 1–(4–Hydroxy –3–Naphthalene Azo–4–Nitro–8–Hydroxy–6–Sulfonic Naphthalene Acid Sodium Salt was synthesized (by the reaction between 3–amino–4– hydroxyl naphthalene and 3 – nitro – 7 – hydroxyl –5– sulfonic naphthalene acid sodium salt and characterized by FTIR technique, its ionization constants (PKs were determined. Synthesis and spectroscopic investigations of its complex with Co (III in aqueous solution revealed the sole formation of (1: 2 (metal: ligand complex. Specral and magnatic studies of the isolated complex indicates octahedral coordination via the N atoms of the azo groups and the O atoms of the hydroxyl groups. The molar conductivity of the complex was determined in an alcoholic solutions indicates that the complex has high molar conductivity. The magnetic properties were determined by using Gouy balance which indicates diamagnetic complex.

  17. The Abiotic Depletion Potential: Background, Updates, and Future

    Directory of Open Access Journals (Sweden)

    Lauran van Oers


    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.

  18. Baseline inventory data users guide to abiotic GIS layers (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...

  19. Abiotic stress responses in plant roots: a proteomics perspective

    Directory of Open Access Journals (Sweden)

    Dipanjana eGhosh


    Full Text Available Abiotic stress conditions adversely affect plant growth, resulting in significant decline in crop productivity. To mitigate and recover from the damaging effects of such adverse environmental conditions, plants have evolved various adaptive strategies at cellular and metabolic levels. Most of these strategies involve dynamic changes in protein abundance that can be best explored through proteomics. This review summarizes comparative proteomic studies conducted with roots of various plant species subjected to different abiotic stresses especially drought, salinity, flood and cold. The main purpose of this article is to highlight and classify the protein level changes in abiotic stress response pathways specifically in plant roots. Shared as well as stressor-specific proteome signatures and adaptive mechanism(s are simultaneously described. Such a comprehensive account will facilitate the design of genetic engineering strategies that enable the development of broad-spectrum abiotic stress-tolerant crops.

  20. Aquatic organism passage at road-stream crossings—synthesis and guidelines for effectiveness monitoring (United States)

    Hoffman, Robert L.; Dunham, Jason B.; Hansen, Bruce P.


    Restoration and maintenance of passage for aquatic organisms at road-stream crossings represents a major management priority, involving an investment of hundreds of millions of dollars (for example, U.S. Government Accounting Office, 2001). In recent years, passage at hundreds of crossings has been restored, primarily by replacing barrier road culverts with bridges or stream simulation culverts designed to pass all species and all life stages of aquatic life and simulate natural hydro-geomorphic processes (U.S. Forest Service, 2008). The current situation has motivated two general questions: 1. Are current design standards for stream simulation culverts adequately re-establishing passage for aquatic biota? and 2. How do we monitor and evaluate effectiveness of passage restoration? To address the latter question, a national workshop was held in March 2010, in Portland, Oregon. The workshop included experts on aquatic organism passage from across the nation (see table of participants, APPENDIX) who addressed four classes of methods for monitoring effectiveness of aquatic organism passage—individual movement, occupancy, demography, and genetics. This report has been written, in part, for field biologists who will be undertaking and evaluating the effectiveness of aquatic organism passage restoration projects at road-stream crossings. The report outlines basic methods for evaluating road-stream crossing passage impairment and restoration and discusses under what circumstances and conditions each method will be useful; what questions each method can potentially answer; how to design and implement an evaluation study; and points out the fundamental reality that most evaluation projects will require special funding and partnerships among researchers and resource managers. The report is organized into the following sections, which can be read independently: 1. Historical context: In this section, we provide a brief history of events leading up to the present situation

  1. Genetic improvement of rice for biotic and abiotic stress tolerance


    ANSARI, MAHMOOD UR RAHMAN; Shaheen, Tayyaba; BUKHARI, SHAZAI; Husnain, Tayyab


    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 crop...

  2. Abiotic stress signalling pathways: specificity and cross-talk. (United States)

    Knight, H; Knight, M R


    Plants exhibit a variety of responses to abiotic stresses that enable them to tolerate and survive adverse conditions. As we learn more about the signalling pathways leading to these responses, it is becoming clear that they constitute a network that is interconnected at many levels. In this article, we discuss the 'cross-talk' between different signalling pathways and question whether there are any truly specific abiotic stress signalling responses.

  3. Conceiving Scenario-Based IS Support for Knowledge Synthesis: The Organization Architect

    Directory of Open Access Journals (Sweden)

    Kam Hou VAT


    Full Text Available This paper examines the idea of creating information systems (IS support for knowledge work through the elaboration of typical organizational scenarios. Specifically, our research is driven by a belief that the design issues of IS support must be situated in the context of social processes in which, in a specific organizational scenario, a particular group of people can conceptualize their knowledge work and hence the purposeful action they wish to undertake. This provides the basis for ascertaining what information support is needed by those who undertake that action, and how modern information technology can help to provide that support. Thereby, designing IS support for knowledge work requires attention to the purposeful action which the IS serves, and hence to the meanings which make those particular actions meaningful and relevant to particular groups of people in a particular situation. This is often facilitated by the provision of an important enquiry process constantly attended to, and integrated into organizational activities by which IS professionals could learn of the organization's continual adjustments to its changing world. Our discussion here brings forth the notion of the learning organization information systems (LOIS, through which each member of the organization is enabled to create his or her own knowledge space, which is subject to some level of description, and thus may be architected and integrated into an organization. Importantly, in order to develop the various LOIS support for knowledge work, we need the correspondent organization scenarios to contextualize the IS design. And we attribute this development philosophy to the essence of systems thinking in conceiving IS support. The paper concludes by reiterating the work of the organization architect, which entails understanding, analyzing, designing, and communicating the most relevant parts of the organization and how they fit together.

  4. Synthesis and post-synthetic modification of amine-, alkyne-, azide- and nitro-functionalized metal-organic frameworks based on DUT-5. (United States)

    Gotthardt, Meike A; Grosjean, Sylvain; Brunner, Tobias S; Kotzel, Johannes; Gänzler, Andreas M; Wolf, Silke; Bräse, Stefan; Kleist, Wolfgang


    Functionalized 4,4'-biphenyldicarboxylic acid molecules with additional amine, alkyne, azide or nitro groups were prepared and applied in the synthesis of novel metal-organic frameworks and mixed-linker metal-organic frameworks isoreticular to DUT-5. The properties of the frameworks could be tuned by varying the number of functional groups in the materials and the amine groups were employed in post-synthetic modification reactions without changing the framework structure or significantly decreasing the porosity of the materials.

  5. Abiotic Stress Responses and Microbe-Mediated Mitigation in Plants: The Omics Strategies. (United States)

    Meena, Kamlesh K; Sorty, Ajay M; Bitla, Utkarsh M; Choudhary, Khushboo; Gupta, Priyanka; Pareek, Ashwani; Singh, Dhananjaya P; Prabha, Ratna; Sahu, Pramod K; Gupta, Vijai K; Singh, Harikesh B; Krishanani, Kishor K; Minhas, Paramjit S


    of plant-microbe interactions that modulate cellular mechanisms in plants under extreme external conditions and help to optimize abiotic stresses. Vigilant amalgamation of these high-throughput approaches supports a higher level of knowledge generation about root-level mechanisms involved in the alleviation of abiotic stresses in organisms.

  6. Abiotic Stress Responses and Microbe-Mediated Mitigation in Plants: The Omics Strategies (United States)

    Meena, Kamlesh K.; Sorty, Ajay M.; Bitla, Utkarsh M.; Choudhary, Khushboo; Gupta, Priyanka; Pareek, Ashwani; Singh, Dhananjaya P.; Prabha, Ratna; Sahu, Pramod K.; Gupta, Vijai K.; Singh, Harikesh B.; Krishanani, Kishor K.; Minhas, Paramjit S.


    of plant–microbe interactions that modulate cellular mechanisms in plants under extreme external conditions and help to optimize abiotic stresses. Vigilant amalgamation of these high-throughput approaches supports a higher level of knowledge generation about root-level mechanisms involved in the alleviation of abiotic stresses in organisms. PMID:28232845

  7. Abiotic and microbial interactions during anaerobic transformations of Fe(II and NOx-

    Directory of Open Access Journals (Sweden)

    Flynn ePicardal


    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

  8. Designing Multidimensional Policing Strategy And Organization: Towards A Synthesis Of Professional And Community Police Models

    Directory of Open Access Journals (Sweden)

    Suve Priit


    Full Text Available In this article we analyse professional police and community policing in view of professionalism, strategy and structures. We aim to find ways for synthesizing these models that are usually seen as incompatible. Unlike many earlier studies of police organizations or strategies, we view strategies in the organization at the corporate, functional and operational levels, and argue that by combining them with functional and divisional principles of structuring, it is possible to place professional strategy at the core of policing, while using the community policing strategy mainly as a component part of the strategy in the framework of divisional organization. This way it is possible to avoid the risk of alienating police from the community and to ensure the successful implementation of corporate strategy through providing professional police units that perform the narrow functions, with quick and adequate information from the community.

  9. Organic Synthesis via Irradiation and Warming of Ice Grains in the Solar Nebula (United States)

    Ciesla, Fred J.; Sanford, Scott A.


    Complex organic compounds, including many important to life on Earth, are commonly found in meteoritic and cometary samples, though their origins remain a mystery. We examined whether such molecules could be produced within the solar nebula by tracking the dynamical evolution of ice grains in the nebula and recording the environments they were exposed to. We found that icy grains originating in the outer disk, where temperatures were less than 30 K, experienced UV irradiation exposures and thermal warming similar to that which has been shown to produce complex organics in laboratory experiments. These results imply that organic compounds are natural byproducts of protoplanetary disk evolution and should be important ingredients in the formation of all planetary systems, including our own.

  10. Rational synthesis of organic thin films with exceptional long-range structural integrity (United States)

    Seiki, Noriya; Shoji, Yoshiaki; Kajitani, Takashi; Ishiwari, Fumitaka; Kosaka, Atsuko; Hikima, Takaaki; Takata, Masaki; Someya, Takao; Fukushima, Takanori


    Highly oriented, domain-boundary-free organic thin films could find use in various high-performance organic materials and devices. However, even with state-of-the-art supramolecular chemistry, it is difficult to construct organic thin films with structural integrity in a size regime beyond the micrometer length scale. We show that a space-filling design, relying on the two-dimensional (2D) nested hexagonal packing of a particular type of triptycene, enables the formation of large-area molecular films with long-range 2D structural integrity up to the centimeter length scale by vacuum evaporation, spin-coating, and cooling from the isotropic liquid of the triptycene. X-ray diffraction analysis and microscopic observations reveal that triptycene molecules form a completely oriented 2D (hexagonal triptycene array) + 1D (layer stacking) structure, which is key for the long-range propagation of structural order.

  11. Organic synthesis via irradiation and warming of ice grains in the solar nebula. (United States)

    Ciesla, Fred J; Sandford, Scott A


    Complex organic compounds, including many important to life on Earth, are commonly found in meteoritic and cometary samples, though their origins remain a mystery. We examined whether such molecules could be produced within the solar nebula by tracking the dynamical evolution of ice grains in the nebula and recording the environments to which they were exposed. We found that icy grains originating in the outer disk, where temperatures were less than 30 kelvin, experienced ultraviolet irradiation exposures and thermal warming similar to that which has been shown to produce complex organics in laboratory experiments. These results imply that organic compounds are natural by-products of protoplanetary disk evolution and should be important ingredients in the formation of all planetary systems, including our own.

  12. Total observed organic carbon (TOOC in the atmosphere: a synthesis of North American observations

    Directory of Open Access Journals (Sweden)

    C. L. Heald


    Full Text Available Measurements of organic carbon compounds in both the gas and particle phases made upwind, over and downwind of North America are synthesized to examine the total observed organic carbon (TOOC in the atmosphere over this region. These include measurements made aboard the NOAA WP-3 and BAe-146 aircraft, the NOAA research vessel Ronald H. Brown, and at the Thompson Farm and Chebogue Point surface sites during the summer 2004 ICARTT campaign. Both winter and summer 2002 measurements during the Pittsburgh Air Quality Study are also included. Lastly, the spring 2002 observations at Trinidad Head, CA, surface measurements made in March 2006 in Mexico City and coincidentally aboard the C-130 aircraft during the MILAGRO campaign and later during the IMPEX campaign off the northwestern United States are incorporated. Concentrations of TOOC in these datasets span more than two orders of magnitude. The daytime mean TOOC ranges from 4.0 to 456 μgC m−3 from the cleanest site (Trinidad Head to the most polluted (Mexico City. Organic aerosol makes up 3–17% of this mean TOOC, with highest fractions reported over the northeastern United States, where organic aerosol can comprise up to 50% of TOOC. Carbon monoxide concentrations explain 46 to 86% of the variability in TOOC, with highest TOOC/CO slopes in regions with fresh anthropogenic influence, where we also expect the highest degree of mass closure for TOOC. Correlation with isoprene, formaldehyde, methyl vinyl ketone and methacrolein also indicates that biogenic activity contributes substantially to the variability of TOOC, yet these tracers of biogenic oxidation sources do not explain the variability in organic aerosol observed over North America. We highlight the critical need to develop measurement techniques to routinely detect total gas phase VOCs, and to deploy comprehensive suites of TOOC instruments in diverse environments to quantify the ambient evolution of organic carbon from source

  13. Enzymatic Synthesis of Esculin Ester in Ionic Liquids Buffered with Organic Solvents

    DEFF Research Database (Denmark)

    Hu, Yifan; Guo, Zheng; Lue, Bena-Marie


    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...... in IL-acetone mixtures made it possible to improve the solubility of esculin while the effects of ILs on lipase activity were minimized. Following the benignity of ILs to lipase activity, the anions of ILs were ranked in the order as [Tf2N](-) > [PF6](-) > [BF4](-) > [CF3SO3](-) > [C4F9SO3](-) > [TAF...

  14. Before the Ring: synthesis of linear organic molecules in astrophysical ices by low energy electron impact (United States)

    Huels, Michael A.; Bass Andrew, D.; Mirsaleh-Kohan, Nasrin; Sanche, Leon

    The question of the origin for the building blocks of life, either synthesized here on earth, or in space [1], has been the subject of much debate, experimental investigation, or astronomical observation, much of it stimulated by the early experiments of Miller [2], and subsequent space radiation related variations thereof [3-5]. And while the precise details of the formation of even the simplest biomolecules that make up life on earth still remain shrouded inmystery, one of the notions that persist throughout the debate is that the building blocks of life, such as amino-acids, or even the cyclic components of RNA and DNA, or other cyclic hydrocarbons (e.g. PHAs), where synthesized via radiolysis [6] either in the earths proto-atmosphere, its early oceans, or in the near interstellar space surrounding the early earth. Here we provide experimental evidence for the hypothesis that interactions of low energy secondary electrons and ions, formed during the radiolysis of matter, with atoms and molecules in the medium, may have played, and may still play an important role in the chemical transformation of astrophysical or planetary surface ices [7], where they lead to the synthesis of more complex chemical species from less complex, naturally occurring components. We report the synthesis and desorption of new chemical species from simple molecular surface ices, containing CH4 / CD4 , C2 D2 , O2 , CO, CO2 , or N2 in various combination mixtures, irradiated by low energy (life's most basic cyclic molecular components in planetary, or astrophysical surface ices that are continuously subjected to the types of space radiations (UV, X-or -ray, or heavy ions) that can generate such low energy secondary electrons. [Funded by NSERC and Canadian Space Agency] [1] P. Ehrenfreund, S. Rasmussen, J. Cleaves, L. Chen, Astrobiology 6 (2006) 490. [2] (a) S.L. Miller, Science 117 (1953) 528; (b) S.L. Miller, J. Am. Chem. Soc. 77 (1955) 2351. [3] (a) M.H. Morre, R.L. Hudson, Icarus 140

  15. Aerosol-assisted synthesis of mesoporous organosilica microspheres with controlled organic contents

    Directory of Open Access Journals (Sweden)

    Yusuke Yamauchi, Norihiro Suzuki, Prashant Gupta, Keisuke Sato, Naoki Fukata, Miwa Murakami, Tadashi Shimizu, Satoru Inoue and Tatsuo Kimura


    Full Text Available Periodic mesoporous organosilica (PMO spherical particles with different organic contents were synthesized in one pot by reacting 1,2-bis(triethoxysilylethane (BTSE with tetraethylorthosilicate (TEOS using a spray-drying technique. The scanning electron microscopy observation of spray-dried products clearly showed the formation of spherical particles. The 29Si magic angle spinning nuclear magnetic resonance data revealed that the organic contents due to ethane fragments embedded in the frameworks were controllable and consistent with the BTSE/TEOS molar ratios of precursor solutions. Transmission electron microscopy, small-angle x-ray scattering, and N2 adsorption data of PMO with controlled organic contents indicated that the ethane fragments were embedded in the frameworks with the formation of ordered mesostructures. PMO with a high organic content (BTSE/TEOS=0.50 only showed a hydrophobic property. According to the same procedure, benzene groups were also integrated to a similar degree in the frameworks by using 1,4-bis(triethoxysilylbenzene.

  16. Quantifying the degradation of organic matter in marine sediments: A review and synthesis

    NARCIS (Netherlands)

    Arndt, S.; Jørgensen, B.B.; LaRowe, D.E.; Middelburg, J.J.; Pancost, R.D.; Regnier, P.


    Quantifying the rates of biogeochemical processes in marine sediments is essential for understanding global element cycles and climate change. Because organic matter degradation is the engine behind benthic dynamics, deciphering the impact that various forces have on this process is central to

  17. Novel approaches for using dehydrogenases and ene-reductases for organic synthesis

    NARCIS (Netherlands)

    Gargiulo, S.


    Oxidation of alcohols is a reaction of major interest for organic chemistry. However, the most common chemical routes developed so far involve the use of toxic or hazardous reagents or catalysts that often lack good chemoselectivity. In this respect, alcohol dehydrogenases (ADHs) represent a very

  18. Independent Synthesis Projects in the Organic Chemistry Teaching Laboratories: Bridging the Gap between Student and Researcher (United States)

    Keller, Valerie A.; Kendall, Beatrice Lin


    Science educators strive to teach students how to be well-rounded scientists with the ability to problem solve, anticipate errors, and adapt to unexpected roadblocks. Traditional organic chemistry experiments seldom teach these skills, no matter how novel or contemporary the subject material. This paper reports on the success of a quarter-long…

  19. Synthesis and Characterization of Calixarene Tetraethers: An Exercise in Supramolecular Chemistry for the Undergraduate Organic Laboratory (United States)

    Debbert, Stefan L.; Hoh, Bradley D.; Dulak, David J.


    In this experiment for an introductory undergraduate organic chemistry lab, students tetraalkylate tertbutylcalix[4]arene, a bowl-shaped macrocyclic oligophenol, and examine the supramolecular chemistry of the tetraether product by proton nuclear magnetic resonance (NMR) spectroscopy. Complexation with a sodium ion reduces the conformational…

  20. Lipase-supported metal-organic framework bioreactor catalyzes warfarin synthesis. (United States)

    Liu, Wan-Ling; Yang, Ni-Shin; Chen, Ya-Ting; Lirio, Stephen; Wu, Cheng-You; Lin, Chia-Her; Huang, Hsi-Ya


    A green and sustainable strategy synthesizes clinical medicine warfarin anticoagulant by using lipase-supported metal-organic framework (MOF) bioreactors (see scheme). These findings may be beneficial for future studies in the industrial production of chemical, pharmaceutical, and agrochemical precursors. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Temperature and soil organic matter decomposition rates - synthesis of current knowledge and a way forward (United States)

    Richard T. Conant; Michael Ryan; Goran I. Agren; Hannah E. Birge; Eric A. Davidson; Peter E. Eliasson; Sarah E. Evans; Serita D. Frey; Christian P. Giardina; Francesca M. Hopkins; Riitta Hyvonen; Miko U. F . Kirschbaum; Jocelyn M. Lavallee; Jens Leifeld; William J. Parton; Jessica Megan Steinweg; Matthew D. Wallenstein; J . A. Martin Wetterstedt; Mark A. Bradford


    The response of soil organic matter (OM) decomposition to increasing temperature is a critical aspect of ecosystem responses to global change. The impacts of climate warming on decomposition dynamics have not been resolved due to apparently contradictory results from field and lab experiments, most of which has focused on labile carbon with short turnover times. But...

  2. Cocrystal Controlled Solid-State Synthesis: A Green Chemistry Experiment for Undergraduate Organic Chemistry (United States)

    Cheney, Miranda L.; Zaworotko, Michael J.; Beaton, Steve; Singer, Robert D.


    Green chemistry has become an important area of concern for all chemists from practitioners in the pharmaceutical industry to professors and the students they teach and is now being incorporated into lectures of general and organic chemistry courses. However, there are relatively few green chemistry experiments that are easily incorporated into…

  3. Determination of Innovation Capability of Organizations: Qualitative Meta Synthesis and Delphi Method

    DEFF Research Database (Denmark)

    Momeni, Mostafa; Nielsen, Susanne Balslev; Kafash, Mahdi Haghighi


    . The innovation capability is associated with other organizational capabilities. So, many organizations have focused on the need to identify innovation capabilities and resources or strengths in relation to external opportunities and threats according to inside-out view because innovation capability has...

  4. Enhancement and assessment of students’ systems thinking skills by application of systemic synthesis questions in the organic chemistry course

    Directory of Open Access Journals (Sweden)

    Hrin Tamara N.


    Full Text Available Many studies in the field of science education have emphasized the fact that systems thinking is a very important higher-order thinking skill which should be fostered during classes. However, more attention has been dedicated to the different ways of systems thinking skills assessment, and less to their enhancement. Taking this into consideration, the goal of our study was not only to validate secondary school students’ systems thinking skills, but also to help students in the complex process of their development. With this goal, new instructional and assessment tools - systemic synthesis questions [SSynQs], were constructed, and an experiment with one experimental (E and one control (C group was conducted during organic chemistry classes. Namely, the instructional teaching/learning method for both E and C groups was the same in processing the new contents, but different on classes for the revision of the selected organic chemistry contents. The results showed that students exposed to the new instructional method (E group achieved higher performance scores on three different types of systems thinking than students from the C group, who were taught by the traditional method. The greatest difference between the groups was found in the most complex dimension of systems thinking construct - in the II level of procedural systems thinking. Along with this dimension, structural systems thinking and I level of procedural systems thinking were also observed. [Projekat Ministarstva nauke Republike Srbije, br. 179010

  5. Facile synthesis of mosquitocidal silver nanoparticles using Mussaenda glabra leaf extract: characterisation and impact on non-target aquatic organisms. (United States)

    Govindarajan, Marimuthu; Rajeswary, Mohan; Hoti, S L; Nicoletti, Marcello; Benelli, Giovanni


    Plant-borne compounds have been proposed for extracellular synthesis of mosquitocidal nanoparticles. However, their impact against mosquito natural enemies has been scarcely studied. Here, we synthesised silver nanoparticles (Ag NPs) using Mussaenda glabra leaf extract as reducing and stabilising agent. Biofabricated Ag NPs were characterised by UV-vis spectrophotometry, X-ray diffraction, Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Compared to the leaf aqueous extract, biosynthesised Ag NPs showed higher toxicity against mosquito vectors Anopheles subpictus, Aedes albopictus and Culex tritaeniorhynchus with LC50 of 17-19 μg/mL, respectively. Ag NPs were found safer to non-target organisms Diplonychus indicus and Gambusia affinis, with respective LC50 values ranging from 1446 to 8628 μg/mL. Overall, M. glabra-fabricated Ag NPs are a promising and eco-friendly tool against larval populations of mosquito vectors of medical and veterinary importance, with negligible toxicity against other non-target aquatic organisms.

  6. Effects of water on reactions for waste treatment, organic synthesis, and bio-refinery in sub- and supercritical water. (United States)

    Akizuki, Makoto; Fujii, Tatsuya; Hayashi, Rumiko; Oshima, Yoshito


    Current research analyzing the effects of water in the field of homogeneous and heterogeneous reactions of organics in sub- and supercritical water are reviewed in this article. Since the physical properties of water (e.g., density, ion product and dielectric constants) can affect the reaction rates and mechanisms of various reactions, understanding the effects that water can have is important in controlling reactions. For homogeneous reactions, the effects of water on oxidation, hydrolysis, aldol condensation, Beckman rearrangement and biomass refining were introduced including recent experimental results up to 100 MPa using special pressure-resistance equipment. For heterogeneous reactions, the effects of ion product on acid/base-catalyzed reactions, such as hydrothermal conversion of biomass-related compounds, organic synthesis in the context of bio-refinery, and hydration of olefins were described and how the reaction paths are controlled by the concentration of water and hydrogen ions was summarized. Copyright © 2013 The Society for Biotechnology, Japan. Published by Elsevier B.V. All rights reserved.

  7. Ionothermal Synthesis of MnAPO-SOD Molecular Sieve without the Aid of Organic Structure-Directing Agents. (United States)

    Liu, Hao; Tian, Zhijian; Wang, Lei; Wang, Yasong; Li, Dawei; Ma, Huaijun; Xu, Renshun


    An SOD-type metalloaluminophosphate molecular sieve (denoted as SOD-Mn) was ionothermally synthesized by introducing manganese(II) cations into the reaction mixture via MnO-acid or MnO2-reductant reactions. Composition and structure analyses results show that two kinds of manganese(II) cations exist in the SOD-Mn structure. Part of the manganese(II) cations isomorphously substitute the framework aluminum(III) with a substitution degree of ∼30%. The rest of the manganese(II) cations occupy a fraction of the sod cages in their hydrated forms. A comprehensive investigation of the synthesis parameters, crystal sizes, and crystallization kinetics indicates that the in situ released hydrated manganese(II) cations direct the formation of SOD-Mn. Such structure-directing effect may be inhibited by both the fluorination of manganese(II) cations and the water accumulation during crystallization. In the fluoride anion-containing reaction mixture with a low ionic liquid content, the crystallization process is strongly suppressed, and large SOD-Mn single crystals of over 200 μm in size are yielded. SOD-Mn is free from organics and shows improved thermal stability compared with metalloaluminophosphates synthesized by using organic structure-directing agents.

  8. Self-Templated Stepwise Synthesis of Monodispersed Nanoscale Metalated Covalent Organic Polymers for In Vivo Bioimaging and Photothermal Therapy. (United States)

    Shi, Yanshu; Deng, Xiaoran; Bao, Shouxin; Liu, Bei; Liu, Bin; Ma, Ping'an; Cheng, Ziyong; Pang, Maolin; Lin, Jun


    Size- and shape-controlled growth of nanoscale microporous organic polymers (MOPs) is a big challenge scientists are confronted with; meanwhile, rendering these materials for in vivo biomedical applications is still scarce. In this study, a monodispersed nanometalated covalent organic polymer (MCOP, M=Fe, Gd) with sizes around 120 nm was prepared by a self-templated two-step solution-phase synthesis method. The metal ions (Fe 3+ , Gd 3+ ) played important roles in generating a small particle size and in the functionalization of the products during the reaction with p-phenylenediamine (Pa). The resultant Fe-Pa complex was used as a template for the subsequent formation of MCOP following the Schiff base reaction with 1,3,5-triformylphloroglucinol (Tp). A high tumor suppression efficiency for this Pa-based COP is reported for the first time. This study demonstrates the potential use of MCOP as a photothermal agent for photothermal therapy (PTT) and also provides an alternative route to fabricate nano-sized MCOPs. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Synthesis of [60]fullerene-ZnO nanocomposite under electric furnace and photocatalytic degradation of organic dyes. (United States)

    Hong, Sung Kyu; Lee, Jeong Ho; Ko, Weon Bae


    Zinc oxide (ZnO) nanoparticles were synthesized by a reaction between an aqueous-alcoholic solution of zinc nitrate and sodium hydroxide under ultrasonic irradiation at room temperature. The morphology, optical properties of the ZnO nanoparticles were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and UV-vis spectroscopy. The [60]fullerene and zinc oxide nanocomposite were synthesized in an electric furnace at 700 degrees C for two hours. The [60]fullerene-ZnO nanocomposite was characterized by XRD, SEM and TEM. In addition, the [60]fullerene-ZnO nanocomposite was investigated as a catalyst in the photocatalytic degradation of organic dyes using UV-vis spectroscopy. The photocatalytic activity of the [60]fullerene-ZnO nanocomposite was compared with that of ZnO nanoparticles, heated ZnO nanoparticles after synthesis, pure [60]fullerene, and heated pure [60]fullerene in organic dyes such as methylene blue (MB), methyl orange (MO), and rhodamine B (RhB) under ultraviolet light at 254 nm.

  10. Fundamental understanding of the synthesis and tribological behavior of organic-inorganic nanoparticles (United States)

    Verma, Arpana

    The objective of this doctoral research is to design, synthesize, and test an advanced lubricant additive using novel active nanostructures of inorganic layered solid lubricant particles (MoS2), integrated and encapsulated with organic molecules, namely triglycerides and phospholipids, respectively. It was hypothesized that this combination can uniquely respond under severe boundary lubrication conditions (where high frictional losses exist). These organic-inorganic nanoparticles were synthesized using a top-down nanomanufacturing process, commonly known as high-energy ball milling or mechanical milling. It was performed in the presence of ambient air followed by organic molecules (triglycerides) to produce nanoparticles with controlled morphologies and surface properties. SEM, particle size analysis, and XRD showed a particle size reduction up to 100 nm and a grain size of 6 nm. TEM showed that after air milling for 48 hrs, agglomerated clusters of quasi-spherical nanoparticles of MoS2 were formed. HRTEM shows that the inter-planar defects and milling assisted shearing between the platelets caused the resultant curling of the planes, forming these unique nanostructures. Further milling of these clusters for 48 hrs in an organic medium (triglycerides) produced mono-dispersed quasi-spherical nanoparticles (lubrication, which is extremely important in a variety of applications including ball bearings, gears, transmissions etc., potentially saving hundreds of millions of dollars from fuel savings, reduced vehicle exhaust emissions and decreased down time, increasing the competitiveness of small and large US manufacturers. Even a modest 1.0% increase in efficiency will have a significant impact on the national economy . Innovations from this project should also benefit key application areas for organic-inorganic material complexes, for example pharmaceuticals, cosmetics and bio-fuels. Keywords/phrases. Advanced Lubricants, Solid Lubricant Nanoparticles, Top

  11. One-Step Synthesis of Hybrid Core-Shell Metal-Organic Frameworks. (United States)

    Yang, Xinyu; Yuan, Shuai; Zou, Lanfang; Drake, Hannah; Zhang, Yingmu; Qin, Junsheng; Alsalme, Ali; Zhou, Hongcai


    Epitaxial growth of MOF-on-MOF composite is an evolving research topic. In current methods, the core-shell MOFs are synthesized via a stepwise strategy which involves growing the shell-MOFs on top of the preformed core-MOFs with matched lattice parameters. However, the inconvenient stepwise synthesis and the strict lattice-matching requirement have limited the development of core-shell MOFs. Herein, we demonstrate that hybrid core-shell MOFs with mismatching lattices can be synthesized under the guidance of nucleation kinetics. A series of MOF composites with mesoporous core and microporous shell were constructed and characterized by optical microscopy, powder X-ray diffraction, gas sorption measurement, and scanning electron microscopy. Isoreticular expansion of microporous shells and orthogonal modification of the core was realized to produce multifunctional MOF composites, which acted as size selective catalysts for olefin epoxidation with high activity and selectivity. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Metabolomics as a Tool to Investigate Abiotic Stress Tolerance in Plants

    Directory of Open Access Journals (Sweden)

    Aurelio Gómez-Cadenas


    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.

  13. Screening for Abiotic Stress Tolerance in Rice: Salt, Cold, and Drought. (United States)

    Almeida, Diego M; Almadanim, M Cecília; Lourenço, Tiago; Abreu, Isabel A; Saibo, Nelson J M; Oliveira, M Margarida


    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.


    Energy Technology Data Exchange (ETDEWEB)

    Beyenal, Haluk [WSU; McLEan, Jeff [JCVI; Majors, Paul [PNNL; Fredrickson, Jim [PNNL


    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.

  15. Synthesis and toxicity evaluation of hydrophobic ionic liquids for volatile organic compounds biodegradation in a two-phase partitioning bioreactor

    Energy Technology Data Exchange (ETDEWEB)

    Rodriguez Castillo, Alfredo Santiago [Ecole Nationale Supérieure de Chimie de Rennes, CNRS, UMR 6226, 11 Allée de Beaulieu, CS 50837, 35708 Rennes Cedex 7 (France); Université européenne de Bretagne (France); Guihéneuf, Solène, E-mail: [Université européenne de Bretagne, Université de Rennes 1, Sciences Chimiques de Rennes, UMR, CNRS 6226, Groupe Ingénierie Chimique & Molécules Pour le Vivant (ICMV), Bât. 10A, Campus de Beaulieu, Avenue du Général Leclerc, CS 74205, 35042 Rennes cedex (France); Le Guével, Rémy [Plate-forme ImPACcell Structure Fédérative de Recherche BIOSIT Université de Rennes 1, Bat. 8, Campus de Villejean, 2 Avenue du Pr. Leon Bernard, CS 34317, 35043 Rennes Cedex (France); Biard, Pierre-François [Ecole Nationale Supérieure de Chimie de Rennes, CNRS, UMR 6226, 11 Allée de Beaulieu, CS 50837, 35708 Rennes Cedex 7 (France); Université européenne de Bretagne (France); and others


    Highlights: • Description of a VOC depollution system suitable with industrial processes, TPPB. • Novel association of TPPB and hydrophobic ionic liquids. • Synthesis of several hydrophobic ionic liquids designed to fit desired properties. • Toxicity evaluation of these ILs towards cells, animals and bacteria. - Abstract: Synthesis of several hydrophobic ionic liquids (ILs), which might be selected as good candidates for degradation of hydrophobic volatile organic compounds in a two-phase partitioning bioreactor (TPPB), were carried out. Several bioassays were also realized, such as toxicity evaluation on activated sludge and zebrafish, cytotoxicity, fluoride release in aqueous phase and biodegradability in order to verify their possible effects in case of discharge in the aquatic environment and/or human contact during industrial manipulation. The synthesized compounds consist of alkylimidazoliums, functionalized imidazoliums, isoqinoliniums, triazoliums, sulfoniums, pyrrolidiniums and morpholiniums and various counter-ions such as: PF{sub 6}{sup −}, NTf{sub 2}{sup −} and NfO{sup −}. Toxicity evaluation on activated sludge of each compound (5% v/v of IL) was assessed by using a glucose uptake inhibition test. Toxicity against zebrafish and cytotoxicity were evaluated by the ImPACCell platform of Rennes (France). Fluoride release in water was estimated by regular measurements using ion chromatography equipment. IL biodegradability was determined by measuring BOD{sub 28} of aqueous samples (compound concentration,1 mM). All ILs tested were not biodegradable; while some of them were toxic toward activated sludge. Isoquinolinium ILs were toxic to human cancerous cell lines. Nevertheless no toxicity was found against zebrafish Danio rerio. Only one IL released fluoride after long-time agitation.

  16. Coordinated Actions of Glyoxalase and Antioxidant Defense Systems in Conferring Abiotic Stress Tolerance in Plants (United States)

    Hasanuzzaman, Mirza; Nahar, Kamrun; Hossain, Md. Shahadat; Mahmud, Jubayer Al; Rahman, Anisur; Inafuku, Masashi; Oku, Hirosuke; Fujita, Masayuki


    Being sessile organisms, plants are frequently exposed to various environmental stresses that cause several physiological disorders and even death. Oxidative stress is one of the common consequences of abiotic stress in plants, which is caused by excess generation of reactive oxygen species (ROS). Sometimes ROS production exceeds the capacity of antioxidant defense systems, which leads to oxidative stress. In line with ROS, plants also produce a high amount of methylglyoxal (MG), which is an α-oxoaldehyde compound, highly reactive, cytotoxic, and produced via different enzymatic and non-enzymatic reactions. This MG can impair cells or cell components and can even destroy DNA or cause mutation. Under stress conditions, MG concentration in plants can be increased 2- to 6-fold compared with normal conditions depending on the plant species. However, plants have a system developed to detoxify this MG consisting of two major enzymes: glyoxalase I (Gly I) and glyoxalase II (Gly II), and hence known as the glyoxalase system. Recently, a novel glyoxalase enzyme, named glyoxalase III (Gly III), has been detected in plants, providing a shorter pathway for MG detoxification, which is also a signpost in the research of abiotic stress tolerance. Glutathione (GSH) acts as a co-factor for this system. Therefore, this system not only detoxifies MG but also plays a role in maintaining GSH homeostasis and subsequent ROS detoxification. Upregulation of both Gly I and Gly II as well as their overexpression in plant species showed enhanced tolerance to various abiotic stresses including salinity, drought, metal toxicity, and extreme temperature. In the past few decades, a considerable amount of reports have indicated that both antioxidant defense and glyoxalase systems have strong interactions in conferring abiotic stress tolerance in plants through the detoxification of ROS and MG. In this review, we will focus on the mechanisms of these interactions and the coordinated action of

  17. Coordinated Actions of Glyoxalase and Antioxidant Defense Systems in Conferring Abiotic Stress Tolerance in Plants

    Directory of Open Access Journals (Sweden)

    Mirza Hasanuzzaman


    Full Text Available Being sessile organisms, plants are frequently exposed to various environmental stresses that cause several physiological disorders and even death. Oxidative stress is one of the common consequences of abiotic stress in plants, which is caused by excess generation of reactive oxygen species (ROS. Sometimes ROS production exceeds the capacity of antioxidant defense systems, which leads to oxidative stress. In line with ROS, plants also produce a high amount of methylglyoxal (MG, which is an α-oxoaldehyde compound, highly reactive, cytotoxic, and produced via different enzymatic and non-enzymatic reactions. This MG can impair cells or cell components and can even destroy DNA or cause mutation. Under stress conditions, MG concentration in plants can be increased 2- to 6-fold compared with normal conditions depending on the plant species. However, plants have a system developed to detoxify this MG consisting of two major enzymes: glyoxalase I (Gly I and glyoxalase II (Gly II, and hence known as the glyoxalase system. Recently, a novel glyoxalase enzyme, named glyoxalase III (Gly III, has been detected in plants, providing a shorter pathway for MG detoxification, which is also a signpost in the research of abiotic stress tolerance. Glutathione (GSH acts as a co-factor for this system. Therefore, this system not only detoxifies MG but also plays a role in maintaining GSH homeostasis and subsequent ROS detoxification. Upregulation of both Gly I and Gly II as well as their overexpression in plant species showed enhanced tolerance to various abiotic stresses including salinity, drought, metal toxicity, and extreme temperature. In the past few decades, a considerable amount of reports have indicated that both antioxidant defense and glyoxalase systems have strong interactions in conferring abiotic stress tolerance in plants through the detoxification of ROS and MG. In this review, we will focus on the mechanisms of these interactions and the coordinated

  18. Synthesis and characterization of low-melting scintillating glass doped with organic activator

    CERN Document Server

    Zhao Hong Sheng; Zhu Dong Mei; Wu Jing


    New colliders for high-energy physics studies require scintillators with short decay time, high density, good radiation hardness and low cost. It is possible to make glass scintillators that can meet these requirements by doping organic scintillating activators into an inorganic glass host. In this research, p-Terphenyl as the activator is doped into lead-tin-fluorophosphate glasses. There is no detectable change of the dopant on the densities and characteristic temperatures of the glass host. The hybrid scintillating glasses doped with p-TP possess 5 ns decay time and a broad fluorescence emission band, the peak of which is at about 545 nm. Although the light yields of the glasses are low, this research shows that it is possible to develop good hybrid scintillating glasses by doping organic activators into inorganic glass host.

  19. Interfacial synthesis of hollow metal-organic framework capsules demonstrating selective permeability (United States)

    Ameloot, Rob; Vermoortele, Frederik; Vanhove, Wim; Roeffaers, Maarten B. J.; Sels, Bert F.; de Vos, Dirk E.


    Metal-organic frameworks (MOFs) are a class of crystalline materials that consist of metal ions and organic ligands linked together by coordination bonds. Because of their porosity and the possibility of combining large surface areas with pore characteristics that can be tailored, these solids show great promise for a wide range of applications. Although most applications currently under investigation are based on powdered solids, developing synthetic methods to prepare defect-free MOF layers will also enable applications based on selective permeation. Here, we demonstrate how the intrinsically hybrid nature of MOFs enables the self-completing growth of thin MOF layers. Moreover, these layers can be shaped as hollow capsules that demonstrate selective permeability directly related to the micropore size of the MOF crystallites forming the capsule wall. Such capsules effectively entrap guest species, and, in the future, could be applied in the development of selective microreactors containing molecular catalysts.

  20. Synthesis of organic soluble poly(substituted-aniline) from 2-methyl-6-ethylaniline tar (United States)

    Liu, Yuan; Li, Shu-Bai; Yao, Pei; Zhang, Qi-Meng


    Organic soluble poly(substituted-aniline) was synthesized by chemical oxidative polymerization from 2-methyl-6-ethylaniline tar. The structural information of samples was characterized using FT-IR and SEM techniques. The influences of acid concentration, mole ratio of oxidants to tar, reaction time and temperature were investigated. The solubility of polymers was also studied. The results indicate that the conductivity of poly(substituted-aniline) could reach 2.51 ×-4 S ṡ cm-1 under the reaction conditions with 1 mol./L hydrochloric acid, mole ratio of oxidants to tar = 1, and at 10∘C for 3 h. The polymers show better solubility than polyaniline in most organic solvents.

  1. Hydrothermal synthesis of Cu-Fe3O4 nanocomposites towards catalytic degradation of organic dyes (United States)

    Han, Jishu; Sun, Xiaoxia; Zhao, Ruiyang; Gao, Hongtao; Wang, Lei


    Degradation of hazardous organic dyes utilizing multifunctional catalytic materials is supposed to be an efficient and promising method. Here, homogeneous Cu-Fe3O4 nanocomposites are synthesized through a facile and versatile one-pot hydrothermal method. The prepared Cu-Fe3O4 possesses spherical structure with rough surface and average diameter of 230 nm. High catalytic activity and structure stability make Cu-Fe3O4 nanocomposites effectively degrade rhodamine B, methylene blue, methyl orange, and congo red. The existence of magnetic Fe3O4 leads the nanocomposites to separate from the solution through external magnet and reuse for cycle degradation. And during the cyclic utilization, Cu-Fe3O4 nanocomposites keep high catalytic activity and, thus, could be used as an efficient degradation catalyst for the application of organic dyes.

  2. Structure in 5's: A Synthesis of the Research on Organization Design


    Henry Mintzberg


    The elements of organizational structuring---which show a curious tendency to appear in five's---suggest a typology of five basic configurations: Simple Structure, Machine Bureaucracy, Professional Bureaucracy, Divisionalized Form, and Adhocracy. The elements include (1) five basic parts of the organization---the operating core, strategic apex, middle line, technostructure, and support staff; (2) five basic mechanisms of coordination---mutual adjustment, direct supervision, and the standardiz...

  3. Impregnated Cobalt, Nickel, Copper and Palladium Oxides on Magnetite: Nanocatalysts for Organic Synthesis


    Pérez Galera, Juana María


    In this manuscript, the application of different nanocatalysts derived from metal oxides impregnated on the surface of the magnetite in different reaction of general interest in Organic Chemistry is described. In the First Chapter, a cobalt derived catalyst was used to study the hydroacylation reaction of azodicarboxylates with aldehydes. In the Second Chapter, a catalyst derived from copper was used to perform different reactions, including homocoupling of terminal alkynes and the subsequent...

  4. Understanding the Configuration of Studies On Virtual Organizations: A Synthesis of Themes for Future Researches

    Directory of Open Access Journals (Sweden)

    Emerson Gomes dos Santos


    Full Text Available The use of new technologies made it possible to improve business and transactions, reinforce cooperation models, strategic alliances and internal and external networks for enterprises. In addition, companies gain competitiveness, innovation and explore new markets. In this context, the virtual organization has become an important research topic. However, given the complexity of the issue several areas have studied virtual organizations under different aspects which may delay the direction and contribution of research on this subject. In order to identify and evaluate the production of recent years, it was possible to understand the recent research configuration to serve as a source for future research opportunities. Therefore, from a systematic literature review, a classification was created to analyze the characteristics of the events and the scientific journals in which these references were published. Despite the systematic method used for the search of references, this study cannot be considered exhaustive and was conducted in order to explore and describe the topics related with cooperation and innovation in virtual organizations. It was observed that, regardless of the channel (event, scientific journal, most of the references is regarded, first, to Computing or Systems and, secondly, to the Management or Production, two areas of study with opportunities for future researches. Theme researchers or new researchers interested in this topic can thus understand the configuration of the studies in approaches with feasibility to be explored in the future.

  5. Nanoarmored Enzymes for Organic Enzymology: Synthesis and Characterization of Poly(2-Alkyloxazoline)-Enzyme Conjugates. (United States)

    Leurs, Melanie; Tiller, Joerg C


    The properties of enzymes can be altered significantly by modification with polymers. Numerous different methods are known to obtain such polymer-enzyme conjugates (PECs). However, there is no universal method to render enzymes into PECs that are fully soluble in organic solvents. Here, we present a method, which achieves such high degree of modification of proteins that the majority of modified enzymes will be soluble in organic solvents. This is achieved by preparing poly(2-alkyloxazoline)s (POx) with an NH 2 end group and coupling this functional polymer via pyromellitic acid dianhydride onto the amino groups of the respective protein. The resulting PECs are capable of serving as surfactants for unmodified proteins, rendering the whole mixture organosoluble. Depending on the nature of the POx and the molecular weight and the nature of the enzyme, the PECs are soluble in chloroform or even toluene. Another advantage of this method is that the poly(2-alkyloxazoline) can be activated with the coupling agent and used for the enzyme conjugation without further purification. The POx-enzyme conjugates generated by this modification strategy show modulated catalytic activity in both, aqueous and organic, systems. © 2017 Elsevier Inc. All rights reserved.

  6. Synthesis and gas adsorption properties of tetra-armed microporous organic polymer networks based on triphenylamine. (United States)

    Yang, Xiao; Yao, Shuwen; Yu, Miao; Jiang, Jia-Xing


    Two novel tetra-armed microporous organic polymers have been designed and synthesized via a nickel-catalyzed Yamamoto-type Ullmann cross-coupling reaction or Suzuki cross-coupling polycondensation. These polymers are stable in various solvents, including concentrated hydrochloric acid, and are thermally stable. The homocoupled polymer YPTPA shows much higher Brunauer-Emmet-Teller-specific surface area up to 1557 m(2) g(-1) than the copolymer SPTPA (544 m(2) g(-1)), and a high CO2 uptake ability of 3.03 mmol g(-1) (1.13 bar/273 K) with a CO2 /N2 sorption selectivity of 17.3:1. Both polymers show high isosteric heats of CO2 adsorption (22.7-26.5 kJ mol(-1)) because the incorporation of nitrogen atoms into the skeleton of microporous organic polymers enhances the interaction between the pore wall and the CO2 molecules. The values are higher than those of the porous aromatic frameworks, which contain neither additional polar functional groups nor nitrogen atoms, and are rather close to those of previously reported microporous organic polymers containing the nitrogen atoms on the pore wall. These data show that these materials would be potential candidates for applications in post-combustion CO2 capture and sequestration technology. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Polyamines and abiotic stress in plants: A complex relationship

    Directory of Open Access Journals (Sweden)

    Rakesh eMinocha


    Full Text Available The physiological relationship between abiotic stress in plants and polyamines was reported more than 40 years ago. Ever since there has been a debate as to whether increased polyamines protect plants against abiotic stress (e.g. due to their ability to deal with oxidative radicals or cause damage to them (perhaps due to hydrogen peroxide produced by their catabolism. The observation that cellular polyamines are typically elevated in plants under both short-term as well as long-term abiotic stress conditions is consistent with the possibility of their dual effects, i.e. being a protector as well as a perpetrator of stress damage to the cells. The observed increase in tolerance of plants to abiotic stress when their cellular contents are elevated by either exogenous treatment with polyamines or through genetic engineering with genes encoding polyamine biosynthetic enzymes is indicative of a protective role for them. However, through their catabolic production of hydrogen peroxide and acrolein, both strong oxidizers, they can potentially be the cause of cellular harm during stress. In fact, somewhat enigmatic but strong positive relationship between abiotic stress and foliar polyamines has been proposed as a potential biochemical marker of persistent environmental stress in forest trees in which phenotypic symptoms of stress are not yet visible. Such markers may help forewarn forest managers to undertake amelioration strategies before the appearance of visual symptoms of stress and damage at which stage it is often too late for implementing strategies for stress remediation and reversal of damage. This review provides a comprehensive and critical evaluation of the published literature on interactions between abiotic stress and polyamines in plants, and examines the experimental strategies used to understand the functional significance of this relationship with the aim of improving plant productivity, especially under conditions of abiotic stress.

  8. Pseudodiploid genome organization AIDS full-length human immunodeficiency virus type 1 DNA synthesis. (United States)

    King, Steven R; Duggal, Nisha K; Ndongmo, Clement B; Pacut, Crystal; Telesnitsky, Alice


    Template switching between copackaged human immunodeficiency virus type 1 (HIV-1) genomic RNAs is genetically silent when identical RNAs are copackaged but yields recombinants when virions contain two distinct RNAs. Sequencing has revealed that errors at retroviral recombination junctions are infrequent, suggesting that template switching is not intrinsically mutagenic. Here, we tested the hypothesis that template switching may instead contribute to replication fidelity. This hypothesis predicts that reverse transcription of a single-copy gene will be more error prone than replication in the presence of a second copy. To test this, HIV-1-based vectors containing both lacZ and the puromycin resistance marker were expressed either alone or with an excess of an "empty" vector lacking lacZ and puro. This resulted in virions with either RNA homodimers or haploid genomes with only a single lacZ-puro RNA. In untreated cells, lacZ inactivation rates suggested that haploid vector reverse transcription was slightly more error prone than that of homodimerized pseudodiploid vectors. Haploid reverse transcription was at least threefold more error prone than pseudodiploid-templated synthesis when slowed by hydroxyurea treatment or stopped prematurely with zidovudine. Individual products of one- and two-copy genes revealed both nucleotide substitutions and deletions, with deletions more frequent than point mutations among haploid genome products. Similar spectra of defective products were observed at early reverse transcription time points and among products of haploid virions. These results indicate that faithful, full-length reverse transcription products were underrepresented in the absence of a reserve of genetic information and suggest that template switching contributes to HIV-1 genomic integrity.

  9. Fast Abiotic Production of Methane at Temperatures Below 100°C (United States)

    Etiope, G.; Ionescu, A.


    Fischer-Tropsch Type (FTT) reactions, e.g., the Sabatier synthesis between H2 and CO2, are considered a main source of abiotic methane on Earth and likely on other planets. Several laboratory FTT experiments demonstrated abiotic CH4 production at temperatures above 200°C, by using Fe, Ni or Cr catalysts, simulating hydrothermal conditions in peridotite-hosted systems in mid-ocean ridges. Nevertheless, at least on laboratory experiment time-scale, Fe-Ni-Cr catalysts do not support CH4 generation at T800 ppmv in 155 mL bottles after 1 day) via Sabatier reaction at 90, 50 and 25°C, using small concentrations of non-pretreated ruthenium (Ru) equivalent to those occurring in chromitites in continental ultramafic rocks (Etiope & Ionescu, 2014; Geofluids, doi:10.1111/gfl.12106). We have repeated the experiments by using 13C-enriched CO2 and we confirm fast production of CH4at percentage levels. The experiments performed so far show that: 1. considerable amounts of CH4can be produced in dry conditions below 100°C with small quantities of Ru; 2. under the same experimental conditions (Sabatier reaction can produce CH4 with a large C isotope fractionation between CO2 and CH4, leading to relatively " light" (13C-depleted) CH4, resembling microbial gas; 4. the CO2-CH4isotope separation decreases over time and by increasing the temperature; 5. minor amounts of C2-C6hydrocarbons are also generated. Our laboratory data are compatible with the isotopic patterns of CH4 naturally occurring in land-based seeps and springs. Our experiments suggest that Ru-enriched chromitites could potentially generate CH4 at low T. Since Ru is reported in Martian meteorites, low T abiotic CH4 production on Mars via Sabatier reaction cannot be excluded (Etiope et al. 2013, Icarus, 224, 276-285).

  10. Synthesis and characterization of low viscosity carbon dioxide binding organic liquids for flue gas clean up

    Energy Technology Data Exchange (ETDEWEB)

    Koech, Phillip K.; Malhotra, Deepika; Heldebrant, David J.; Cantu Cantu, David; Glezakou, Vassiliki Alexandra; Rousseau, Roger J.


    Climate change is partly attributed to global anthropogenic carbon dioxide (CO2) emission to the atmosphere. These environmental effects can be mitigated by CO2 capture, utilization and storage. Alkanolamine solvents, such as monoethanolamine (MEA), which bind CO2 as carbamates or bicarbonate salts are used for CO2 capture in niche applications. These solvents consist of approximately 30 wt% of MEA in water, exhibiting a low, CO2-rich viscosity, fast kinetics and favorable thermodynamics. However, these solvents have low CO2 capacity and high heat capacity of water, resulting in prohibitively high costs of thermal solvent regeneration. Effective capture of the enormous amounts of CO2 produced by coal-fired plants requires a material with high CO2 capacity and low regeneration energy requirements. To this end, several water-lean transformational solvents systems have been developed in order to reduce these energy penalties. These technologies include nano-material organic hybrids (NOHMs), task-specific, protic and conventional ionic liquids, phase change solvents. As part of an ongoing program in our group, we have developed new water lean transformational solvents known as CO2 binding organic liquids (CO2BOLs) which have the potential to be energy efficient CO2 capture solvents. These solvents, also known as switchable ionic liquids meaning, are organic solvents that can reversibly transform from non- ionic to ionic form and back. The zwitterionic state in these liquids is formed when low polarity non-ionic alkanolguanidines or alkanolamidines react with CO2 or SO2 to form ionic liquids with high polarity. These polar ionic liquids can be thermally converted to the less polar non-ionic solvent by releasing CO2.

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

    DEFF Research Database (Denmark)

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


    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...... for modification toward solubility and functionalization are described. The electronic CD spectra of the tube and molecular intermediates are correlated with theoretical spectra calculated with time-dependent density functional theory to characterize the chirality of the tube. Both experimental (NMR-titrations...

  12. Synthesis and Characterization of Organic Dyes Containing Various Donors and Acceptors (United States)

    Wu, Tzi-Yi; Tsao, Ming-Hsiu; Chen, Fu-Lin; Su, Shyh-Gang; Chang, Cheng-Wen; Wang, Hong-Paul; Lin, Yuan-Chung; Ou-Yang, Wen-Chung; Sun, I-Wen


    New organic dyes comprising carbazole, iminodibenzyl, or phenothiazine moieties, respectively, as the electron donors, and cyanoacetic acid or acrylic acid moieties as the electron acceptors/anchoring groups were synthesized and characterized. The influence of heteroatoms on carbazole, iminodibenzyl and phenothiazine donors, and cyano-substitution on the acid acceptor is evidenced by spectral, electrochemical, photovoltaic experiments, and density functional theory calculations. The phenothiazine dyes show solar-energy-to-electricity conversion efficiency (η) of 3.46–5.53%, whereas carbazole and iminodibenzyl dyes show η of 2.43% and 3.49%, respectively. PMID:20162019

  13. A porous Cu(II) metal-organic framework: Synthesis, crystal structure and gas adsorption properties (United States)

    Li, Wu-Wu; Guo, Ying; Zhang, Wei-Hong


    Presented here is a new porous Cu(II) metal-organic framework, namely [Cu(tdc)(H2O)]n·n(DMA) (1 H2tdc = thiophene-2,5-dicarboxylic acid, DMA = N,N‧-dimethylacetamide), which was obtained by the self-assembly reaction of CuCl2 and H2tdc under solvothermal conditions. Single crystal X-ray diffraction analysis revealed that compound 1 features a 3D porous framework based on 1D chain structure subunits, and the 1D rhombohedral channels are occupied by the lattice DMA molecules. Gas adsorption studies reveal that this desolvated sample exhibit high uptake capacity for light hydrocarbons.

  14. Prebiological Synthesis Organic Matter and Origin of Life in Protoplanetary Disks (United States)

    Snytnikov, V. N.


    Processes and conditions around new born Sun and possibly other young stars led to the origin of life in the circumstellar disc in a few million years. Than the circumsolar biosphere evolved to its current earth state. In agreement with the main results of the natural sciences and the theory of self-organization, several stages are necessary for the life to emerge on the Earth. Nowday we can specify "The cold prehistiry of the life", "RNA-world", "Preplanet biosphere", "Destructive biosphere", "Earth of bacteria".

  15. Synthesis and Characterization of Organic Dyes Containing Various Donors and Acceptors

    Directory of Open Access Journals (Sweden)

    Wen-Chung Ou-Yang


    Full Text Available New organic dyes comprising carbazole, iminodibenzyl, or phenothiazine moieties, respectively, as the electron donors, and cyanoacetic acid or acrylic acid moieties as the electron acceptors/anchoring groups were synthesized and characterized. The influence of heteroatoms on carbazole, iminodibenzyl and phenothiazine donors, and cyano-substitution on the acid acceptor is evidenced by spectral, electrochemical, photovoltaic experiments, and density functional theory calculations. The phenothiazine dyes show solar-energy-to-electricity conversion efficiency (η of 3.46–5.53%, whereas carbazole andiminodibenzyl dyesshow η of 2.43% and 3.49%, respectively.

  16. Templated synthesis, postsynthetic metal exchange, and properties of a porphyrin-encapsulating metal-organic material

    KAUST Repository

    Zhang, ZhenJie


    Reaction of biphenyl-3,4′,5-tricarboxylate (H 3BPT) and CdCl 2 in the presence of meso-tetra(N-methyl-4-pyridyl)porphine tetratosylate (TMPyP) afforded porph@MOM-10, a microporous metal-organic material containing CdTMPyP cations encapsulated in an anionic Cd(II) carboxylate framework, [Cd 6(BPT) 4Cl 4(H 2O) 4]. Porph@MOM-10 is a versatile platform that undergoes exchange to serve as the parent of a series of porph@MOMs that exhibit permanent porosity and heterogeneous catalytic activity. © 2011 American Chemical Society.

  17. Synthesis and characterization of naphthalene end-capped triethylsilylethynyl anthradithiophene for organic thin-film transistors

    Energy Technology Data Exchange (ETDEWEB)

    Ha, Yeon Hee; Koh, Hye Jin; Shin, Sung Chul; Kim, Yun Hi [Gyeongsang National University, Jinju (Korea, Republic of)


    Naphthalene end-capped triethylsilylethynyl anthradithiophene was synthesized by a Suzuki coupling reaction. The obtained compound had good solubility due to its bulky triethylsilylethynyl groups although the extended π-conjugated backbone structure. The thermal stability of the new material was analyzed by thermogravimetry analysis and differential scanning calorimeter thermograms. The optical and electrochemical properties were examined. A thin film of compound was fabricated by spin-coating and exhibited p-channel organic thin film transistors (OTFTs) transport with hole mobility of 4 x 10{sup -4} cm{sup 2}/Vs.

  18. Design and Synthesis of Novel Porous Metal-Organic Frameworks (MOFs) Toward High Hydrogen Storage Capacity

    Energy Technology Data Exchange (ETDEWEB)

    Mohamed, Eddaoudi [USF; Zaworotko, Michael [USF; Space, Brian [USF; Eckert, Juergen [USF


    Statement of Objectives: 1. Synthesize viable porous MOFs for high H2 storage at ambient conditions to be assessed by measuring H2 uptake. 2. Develop a better understanding of the operative interactions of the sorbed H2 with the organic and inorganic constituents of the sorbent MOF by means of inelastic neutron scattering (INS, to characterize the H2-MOF interactions) and computational studies (to interpret the data and predict novel materials suitable for high H2 uptake at moderate temperatures and relatively low pressures). 3. Synergistically combine the outcomes of objectives 1 and 2 to construct a made-to-order inexpensive MOF that is suitable for super H2 storage and meets the DOE targets - 6% H2 per weight (2kWh/kg) by 2010 and 9% H2 per weight (3kWh/kg) by 2015. The ongoing research is a collaborative experimental and computational effort focused on assessing H2 storage and interactions with pre-selected metal-organic frameworks (MOFs) and zeolite-like MOFs (ZMOFs), with the eventual goal of synthesizing made-to-order high H2 storage materials to achieve the DOE targets for mobile applications. We proposed in this funded research to increase the amount of H2 uptake, as well as tune the interactions (i.e. isosteric heats of adsorption), by targeting readily tunable MOFs:

  19. Synthesis and characterization of organic intercalated layered double hydroxides and their application in bitumen modification

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Song [State Key Laboratory of Silicate Materials for Architectures, Wuhan University of Technology, Wuhan 430070 (China); Yu, Jianying, E-mail: [State Key Laboratory of Silicate Materials for Architectures, Wuhan University of Technology, Wuhan 430070 (China); Sun, Yubin [Center for Materials Research and Analysis, Wuhan University of Technology, Wuhan 430070 (China); Wu, Shaopeng [State Key Laboratory of Silicate Materials for Architectures, Wuhan University of Technology, Wuhan 430070 (China)


    Organic layered double hydroxides (LDHs) intercalated by sodium dodecylbenzenesulfonate (SDBS) were prepared by anion-exchange method and applied to modify bitumen aiming at improving ageing resistance of bitumen. The organic LDHs (SDBS–LDHs) were characterized by X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM) and Ultraviolet and visible (UV–vis) spectrophotometry. The effect of SDBS–LDHs and LDHs on physical and anti-ageing properties of bitumen was evaluated by means of conventional and rheological test. The results of XRD, FTIR and SEM show that SDBS is successfully intercalated into interlayer of LDHs, and the UV–vis reflectance and absorbance curves illustrate that intercalation of SDBS enhances the UV shielding effect of LDHs. The addition of SDBS–LDHs or LDHs has little influence on physical properties of bitumen because SDBS–LDHs and LDHs are physically mixed in bitumen. Compared with pristine bitumen after TFOT and UV irradiation ageing, the introduction of SDBS–LDHs and LDHs significantly improves thermal- and photo-oxidative ageing resistance of bitumen. Notably, bitumen with SDBS–LDHs exhibits better anti-ageing performance than that with LDHs, implying more effective modification of SDBS-LDHs which is due to the enhanced UV protective ability and compatibility with bitumen of SDBS–LDHs. - Highlights: • XRD, FTIR and SEM were used to confirm the successful intercalation. • SDBS–LDHs show superior UV protective ability. • SDBS–LDHs improved the anti-ageing properties of bitumen.

  20. Simple Organic Molecules as Catalysts for Enantioselective Synthesis of Amines and Alcohols (United States)

    Silverio, Daniel L.; Torker, Sebastian; Pilyugina, Tatiana; Vieira, Erika M.; Snapper, Marc L.; Haeffner, Fredrik; Hoveyda, Amir H.


    The discovery of new catalysts that can generate complex organic compounds via enantioselective transformations is central to advances in the life sciences;i for this reason, many chemists try to discover catalysts that can be used to produce chiral molecules with a strong preference for one mirror image isomer.ii The ideal catalyst should be devoid of precious elementsiii and should bring reactions to completion in a few hours using operationally simple procedures. In this manuscript, we introduce a set of small organic molecules that can catalyze reactions of unsaturated organoboron reagents with imines and carbonyls; the products of the reactions are enantiomerically pure amines and alcohols, which can be used to synthesize more complex, biologically active molecules. A distinguishing feature of this new catalyst class is the presence of a 'key' proton embedded within their structure. The catalyst is derived from the abundant amino acid valine and was prepared in large quantities in four steps using inexpensive reagents. Reactions are scalable, do not demand stringent conditions, and can be performed with as little as 0.25 mol % catalyst in less than six hours at room temperature to generate products in >85% yield and ≥97:3 enantiomeric ratio. The efficiency, selectivity and operational simplicity of the transformations and the range of boron-based reagents render this advance vital to future progress in chemistry, biology and medicine. PMID:23407537

  1. All Rodents Are Not the Same: A Modern Synthesis of Cortical Organization (United States)

    Krubitzer, Leah; Campi, Katharine L.; Cooke, Dylan F.


    Rodents are a major order of mammals that is highly diverse in distribution and lifestyle. Five suborders, 34 families, and 2,277 species within this order occupy a number of different niches and vary along several lifestyle dimensions such as diel pattern (diurnal vs. nocturnal), terrain niche, and diet. For example, the terrain niche of rodents includes arboreal, aerial, terrestrial, semi-aquatic, burrowing, and rock dwelling. Not surprisingly, the behaviors associated with particular lifestyles are also highly variable and thus the neocortex, which generates these behaviors, has undergone corresponding alterations across species. Studies of cortical organization in species that vary along several dimensions such as terrain niche, diel pattern, and rearing conditions demonstrate that the size and number of cortical fields can be highly variable within this order. The internal organization of a cortical field also reflects lifestyle differences between species and exaggerates behaviorally relevant effectors such as vibrissae, teeth, or lips. Finally, at a cellular level, neuronal number and density varies for the same cortical field in different species and is even different for the same species reared in different conditions (laboratory vs. wild-caught). These very large differences across and within rodent species indicate that there is no generic rodent model. Rather, there are rodent models suited for specific questions regarding the development, function, and evolution of the neocortex. PMID:21701141

  2. Synthesis, fine structural characterization, and CO2 adsorption capacity of metal organic frameworks-74. (United States)

    Adhikari, Abhijit Krishna; Lin, Kuen-Song


    Two metal organic frameworks of MOF-74 group (zinc and copper-based) were successfully synthesized, characterized, and evaluated for CO2 adsorption. The both samples such as MOF-74(Zn) and MOF-74(Cu) were characterized with FE-SEM for morphology and particle size, XRD patterns for phase structure, FTIR for organic functional groups, nitrogen adsorption for pore textural properties, and X-ray absorption spectroscopy for fine structural parameters and oxidation states of central metal atoms. CO2 adsorption isotherms of MOF-74 samples were measured in a volumetric adsorption unit at 273 K and pressure up to 1.1 bar. The MOF-74(Zn) and MOF-74(Cu) adsorbents have the pore widths of 8.58 and 8.04 angstroms with the BET specific surface areas of 1,474 and 1,345 m2 g(-1), respectively. CO2 adsorption capacities of MOF-74(Zn) and MOF-74(Cu) were 4.10 and 3.38 mmol x g(-1), respectively measured at 273 K and 1.1 bar. The oxidation state of central atoms in MOF-74(Zn) was Zn(II) confirmed by XANES spectra while MOF-74(Cu) was composed of Cu(I) and Cu(II) central atoms. The bond distances of Zn--O and Cu--O were 1.98 and 1.94 angstroms, respectively.

  3. Synthesis of Amphiphilic Hyperbranched AIE-active Fluorescent Organic Nanoparticles and Their Application in Biological Application. (United States)

    Lv, Qiulan; Wang, Ke; Xu, Dazhuang; Liu, Meiying; Wan, Qing; Huang, Hongye; Liang, Shangdong; Zhang, Xiaoyong; Wei, Yen


    Aggregation-induced emission (AIE) dyes have recently attracted much attention for biomedical applications for their remarkable AIE properties. However, the hydrophobic nature of AIE dyes made them difficult to be dispersed in physiological solution and problematic for biomedical application directly. Great efforts have been made to overcome this problem, and different strategies for preparation of water dispersible AIE based nanoprobes had been explored previously. However, a facile and effective strategy is still highly desirable and of great importance for the biomedical applications of AIE dye based on nanoprobes. In this work, the fabrication of amphiphilic hyperbranched fluorescent organic nanoparticles with a core-shell structure based on an AIE dye [tetraphenylethene acrylate (TPE-O-E)] and a hyperbranched polyamino compound [polyethylene imine (PEI)] through Michael addition reaction is described for the first time. The AIE dye as well as the final product PEI-TPE-O-E was characterized in detail by a number of techniques. To test their biomedical application potential, the cell viability as well as cell imaging properties of the PEI-TPE-O-E was also examined. The results showed that the PEI-TPE-O-E organic nanoparticles presented high water dispersiblity, ultrabright fluroerescence, low cytotoxicity and excellent biocompatibility, making them promising for biological imaging and gene delivery applications. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Abiotic sulfide oxidation via manganese reduction fuels the deep biosphere (United States)

    Bottrell, S.; Böttcher, M. E.; Schippers, A.; Parkes, R.; Raiswell, R.


    The deep biosphere in marine sediments consists of large populations of metabolically active Bacteria and Archaea [1, 2]. Buried organic carbon is the main energy source for the deep biosphere and is anaerobically oxidized via nitrate-, Mn(IV)-, Fe(III)-, sulfate or carbonate-reduction. Sulfate reduction has been identified as the most important of these processes [3, 4] yet sulfate is typically quantitatively removed from pore waters in the upper few meters of marine sediments. A key question remains: “How is continued metabolic activity maintained in the deep biosphere?”. Buried organic carbon remains as an electron donor but the source of electron acceptors is less clear. Stable isotope compositions of sulfur and oxygen in sulfate are particularly useful in the study of biogeochemical processes and sediment-pore fluid interactions e.g. [5, 6]. Here we use stable sulfur and oxygen isotope compositions to show that the oxidant sulfate is generated by anoxic sulfide oxidation in deeply buried sediments of the Cascadia margin and Blake Ridge and controlled anoxic experiments to constrain the mechanisms involved on this reaction. Pore fluid sulfate in deep Cascadia margin and Blake Ridge sediments contained sulfur with similar isotopic composition to diagenetic sulfide in the sediment and oxygen that was depleted in 18O (in some cases depleted in 18O relative to pore water). Experiments with Mn(IV)-containing oxides confirmed that these can abiotically oxidize iron sulfides and also produce sulfate depleted in 18O relative to water. In another set of anoxic experiments, pyrite was mixed with different Fe(III) minerals. Crucially, experiments with synthesized pure Fe(III) minerals produced no sulfate but identical experiments with natural Fe(III) minerals containing trace Mn did. Sulfate concentrations in solution were stoichiometrically balanced by Mn concentrations, showing trace Mn(IV) in the natural minerals to be the oxidizing agent generating sulfate

  5. Abiotic and microbiotic factors controlling biofilm formation by thermophilic sporeformers. (United States)

    Zhao, Yu; Caspers, Martien P M; Metselaar, Karin I; de Boer, Paulo; Roeselers, Guus; Moezelaar, Roy; Nierop Groot, Masja; Montijn, Roy C; Abee, Tjakko; Kort, Remco


    One of the major concerns in the production of dairy concentrates is the risk of contamination by heat-resistant spores from thermophilic bacteria. In order to acquire more insight in the composition of microbial communities occurring in the dairy concentrate industry, a bar-coded 16S amplicon sequencing analysis was carried out on milk, final products, and fouling samples taken from dairy concentrate production lines. The analysis of these samples revealed the presence of DNA from a broad range of bacterial taxa, including a majority of mesophiles and a minority of (thermophilic) spore-forming bacteria. Enrichments of fouling samples at 55°C showed the accumulation of predominantly Brevibacillus and Bacillus, whereas enrichments at 65°C led to the accumulation of Anoxybacillus and Geobacillus species. Bacterial population analysis of biofilms grown using fouling samples as an inoculum indicated that both Anoxybacillus and Geobacillus preferentially form biofilms on surfaces at air-liquid interfaces rather than on submerged surfaces. Three of the most potent biofilm-forming strains isolated from the dairy factory industrial samples, including Geobacillus thermoglucosidans, Geobacillus stearothermophilus, and Anoxybacillus flavithermus, have been characterized in detail with respect to their growth conditions and spore resistance. Strikingly, Geobacillus thermoglucosidans, which forms the most thermostable spores of these three species, is not able to grow in dairy intermediates as a pure culture but appears to be dependent for growth on other spoilage organisms present, probably as a result of their proteolytic activity. These results underscore the importance of abiotic and microbiotic factors in niche colonization in dairy factories, where the presence of thermophilic sporeformers can affect the quality of end products.

  6. Synthesis, structure and characterization of five new organically templated metal sulfates with 2-aminopyridinium. (United States)

    Bednarchuk, Tamara J; Kinzhybalo, Vasyl; Pietraszko, Adam


    The chemistry of organically templated metal sulfates has attracted interest from the materials science community and the development of synthetic strategies for the preparation of organic-inorganic hybrid materials with novel structures and special properties is of current interest. Sulfur-oxygen-metal linkages provide the possibility of using sulfate tetrahedra as building units to form new solid-state materials. A series of novel organically templated metal sulfates of 2-aminopyridinium (2ap) with aluminium(III), cobalt(II), magnesium(II), nickel(II) and zinc(II) were obtained from the respective aqueous solutions and studied by single-crystal X-ray diffraction. The compounds crystallize in centrosymmetric triclinic unit cells in three structure types: type 1 for 2-aminopyridinium hexaaquaaluminium(III) bis(sulfate) tetrahydrate, (C5H7N2)[Al(H2O)6](SO4)2·4H2O, (I); type 2 for bis(2-aminopyridinium) tris[hexaaquacobalt(II)] tetrakis(sulfate) dihydrate, (C5H7N2)2[Co(H2O)6]3(SO4)4·2H2O, (II), and bis(2-aminopyridinium) tris[hexaaquamagnesium(II)] tetrakis(sulfate) dihydrate, (C5H7N2)2[Mg(H2O)6]3(SO4)4·2H2O, (III); and type 3 for bis(2-aminopyridinium) hexaaquanickel(II) bis(sulfate), (C5H7N2)2[Ni(H2O)6](SO4)2, (IV), and bis(2-aminopyridinium) hexaaquazinc(II) bis(sulfate), (C5H7N2)2[Zn(H2O)6](SO4)2, (V). The templating role of the 2ap cation in all of the reported crystalline substances is governed by the formation of characteristic charge-assisted hydrogen-bonded pairs with sulfate anions and the presence of π-π interactions between the cations. Additionally, both coordinated and uncoordinated water molecules are involved in hydrogen-bond formation. As a consequence, extensive three-dimensional hydrogen-bonding patterns are formed in the reported crystal structures.

  7. Trapping Planetary Noble Gases During the Fischer-Tropsch-Type Synthesis of Organic Materials (United States)

    Nuth, Joseph A.; Johnson, N. M.; Meshik, A.


    When hydrogen, nitrogen and CO arc exposed to amorphous iron silicate surfaces at temperatures between 500 - 900K, a carbonaceous coating forms via Fischer-Tropsch type reactions!, Under normal circumstances such a catalytic coating would impede or stop further reaction. However, we find that this coating is a better catalyst than the amorphous iron silicates that initiate these rcactions:u . The formation of a self-perpetuating catalytic coating on grain surfaces could explain the rich deposits of macromolecular carbon found in primitive meteorites and would imply that protostellar nebulae should be rich in organic materiaL Many more experiments are needed to understand this chemical system and its application to protostellar nebulae.

  8. Rhenium(I) terpyridine complexes - synthesis, photophysical properties and application in organic light emitting devices. (United States)

    Klemens, Tomasz; Świtlicka-Olszewska, Anna; Machura, Barbara; Grucela, Marzena; Schab-Balcerzak, Ewa; Smolarek, Karolina; Mackowski, Sebastian; Szlapa, Agata; Kula, Slawomir; Krompiec, Stanisław; Lodowski, Piotr; Chrobok, Anna


    Six new Re(i) complexes of the general formula [ReCl(CO)3(4'-R-terpy-κ(2)N)] with 2,2':6',2''-terpyridine-based ligands have been synthesized and characterized by IR, NMR ((1)H and (13)C), UV-Vis spectroscopy and single crystal X-ray analysis. The luminescent properties of [ReCl(CO)3(4'-R-terpy-κ(2)N)] were studied in solution and solid state, at 298 and 77 K, respectively. To obtain detailed insight into the electronic structures and spectroscopic properties of [ReCl(CO)3(4'-R-terpy-κ(2)N)], the density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations were performed. Also, the suitability of this class of materials for being applied in organic light emitting diodes (OLEDs) has been preliminarily tested.

  9. Synthesis, spectral studies and catalytic activity of ruthenium(II) complexes with organic amide ligands

    Energy Technology Data Exchange (ETDEWEB)

    Ashok, More; Prasad, Adapa V.S.S.; Ravinder, Vadde [Kakatiya University, Warangal (India). Dept. of Chemistry]. E-mail:


    Twelve new hexacoordinated ruthenium(II) complexes with organic amides, [RuH(CO)(PPh{sub 3}){sub 2}(L{sub 2})], have been synthesized by treating the precursor, [RuH{sub 2}(CO)(PPh{sub 3}){sub 3}], with twelve different amide proligands separately. These complexes were characterized by elemental analysis and by UV-vis, IR, {sup 1}H, {sup 13}C and {sup 31}P NMR spectroscopies. Molecular formulae and octahedral structures have been tentatively proposed for the products. These complexes were found to be efficient in the catalytic reduction of NO{sub 2}-containing drugs such as chloramphenicol and metronidazole to their amino derivatives. The percent yields of the reduction products were determined spectrophotometrically. (author)

  10. Photocatalytic degradation of organic pollutant aldicarb by non-metal-doped nanotitania: synthesis and characterization. (United States)

    Kattiparambil Manoharan, Rajesh; Sankaran, Sugunan


    The current study focused on pollution control by titania through photocatalytic degradation of aldicarb pesticide in aqueous medium. Titania, which is an efficient photocatalyst, can bring about degradation of aqueous organic pollutants under UV and visible light irradiation. Here, we prepared titania by sol-gel method from titanium tetraisopropoxide and doped non-metals like N and S from sources such as urea and thiourea, respectively. The prepared catalyst was characterized by XRD, UV-Vis.DRS, TEM, XPS, etc. Photocatalytic activity of the catalyst was evaluated from extend of degradation of aldicarb pesticide by measuring its concentration with the help of HPLC. It was found that the modified catalyst showed better photocatalytic degradation than pure titania in visible light.

  11. Electron beam synthesis of metal and semiconductor nanoparticles using metal-organic frameworks as ordered precursors (United States)

    Jacobs, Benjamin W.; Houk, Ronald J. T.; Wong, Bryan M.; Talin, A. Alec; Allendorf, Mark D.


    We demonstrate a versatile, bottom-up method of forming metal and semiconducting nanoparticles by exposing precursor metal-organic frameworks (MOFs) to an electron beam. Using a transmission electron microscope to initiate and observe growth, we show that the composition, size, and morphology of the nanoparticles are determined by the chemistry and structure of the MOF, as well as the electron beam properties. Zinc oxide, metallic indium and copper particles were produced with narrow and tunable size distributions comparable to those obtained from state-of-the-art methods. This method represents a first step toward the fabrication of nanoscale heterostructures using the highly controlled environment of the MOF pores as a scaffold or template.

  12. Synthesis and structure of new carbohydrate metal-organic frameworks and inclusion complexes (United States)

    Sha, Jing-Quan; Wu, Lian-He; Li, Shu-Xian; Yang, Xiao-Ning; Zhang, Yu; Zhang, Qian-Nan; Zhu, Pei-Pei


    Two new metal-organic framework compounds based on natural β-cyclodextrin molecules (β-CD) and alkali metals (Na+/K+) were synthesized and characterized by elemental analyses, IR, XPRD and 1HNMR. Single-crystal X-ray diffraction analysis reveals that compounds 1 and 2 possess the bowl-like pore and the "8" type double channels configuration. Due to the [blow + channel] double configuration, 5-Fluorouracil (5-FU) and Quercetin inclusion complexes of compound 1 are studied, and the results show that the two kinds of drug with different structure and size can be included into the compound at the same time, which is expected to become a new type of multi-functional green crystalline solid material.

  13. Studies on the chemical synthesis and characterization of lead oxide nanoparticles with different organic capping agents

    Energy Technology Data Exchange (ETDEWEB)

    Arulmozhi, K. T., E-mail: [Physics Wing (DDE), Annamalai University, Tamil Nadu, India - 608 002 (India); Mythili, N. [Department of Physics, Annamalai University, Tamil Nadu, India - 608 002 (India)


    Lead oxide (PbO) nanoparticles were chemically synthesized using Lead (II) acetate as precursor. The effects of organic capping agents such as Oleic acid, Ethylene Diamine Tetra Acetic acid (EDTA) and Cetryl Tri Methyl Butoxide (CTAB) on the size and morphology of the nanoparticles were studied. Characterization techniques such as X-ray diffraction (XRD), Fourier Transform-Infrared spectroscopy (FT-IR), Photoluminescence (PL) Field Emission Scanning Electron Microscopy (FE-SEM), Energy Dispersive Spectroscopy (EDS) and Transmission Electron Microscopy (TEM) were used to analyse the prepared nanoparticles for their physical, structural and optical properties. The characterization studies reveal that the synthesized PbO nanoparticles had well defined crystalline structure and sizes in the range of 25 nm to 36 nm for capping agents used and 40 nm for pure PbO nanoparticles.

  14. Synthesis of yellow emitting bis-pyrimidine based purely organic phosphors

    Energy Technology Data Exchange (ETDEWEB)

    Kumar, Vinod, E-mail: [Department of Physics, University of the Free State, Bloemfontein, PO Box 9300 (South Africa); Gohain, Mukut [Department of Chemistry, University of the Free State, Bloemfontein, PO Box 9300 (South Africa); Kumar, Vijay [Department of Physics, University of the Free State, Bloemfontein, PO Box 9300 (South Africa); Van Tonder, Johannes H.; Bezuidenhoudt, Barend C.B. [Department of Chemistry, University of the Free State, Bloemfontein, PO Box 9300 (South Africa); Ntwaeaborwa, O.M. [Department of Physics, University of the Free State, Bloemfontein, PO Box 9300 (South Africa); Swart, Hendrik C., E-mail: [Department of Physics, University of the Free State, Bloemfontein, PO Box 9300 (South Africa)


    Two organic phosphors 5,5'-(4-pyridinylmethylene)bis[1,3-dimethyl-2,4,6-(1H,3H,5H) -pyrimidinetrione] (BP) and 5,5'-(4-nitrophenylmethylene)bis[1,3-dimethyl-2,4,6-(1H,3H,5H) -pyrimidinetrione] (BP-NO{sub 2}) have been synthesized through a one pot reaction of N,N-dimethylbarbituric acid and pyridine aldehyde in acetonitrile at 80 °C. The synthesized phosphors were characterized by single-crystal X-ray crystallography, Fourier transform infrared spectroscopy, UV–vis spectroscopy, thermogravimetry analysis and photoluminescence (PL) spectroscopy. A broadband PL emission spectrum ranging from 400 to 800 nm was recorded from both phosphors. The BP showed a luminescence peak at ca. 560 nm (2.21 eV), while the BP-NO{sub 2} exhibited a peak at 590 nm (2.1 eV), which reflect pure yellow emissions. The optimized geometry of the phosphors has been studied with a quantum chemical approach using the density functional theory. The highest occupied and lowest unoccupied molecular orbitals are predicted from the calculations. - Highlights: • Two stable organic phosphors to bridge the yellow gap were synthesized. • PL emission spectrum ranging from 400 to 800 nm was recorded for both. • Luminescence peaks were obtained at 560 nm (2.21 eV) and 590 nm (2.1 eV). • The optimized geometry was obtained with a quantum chemical approach using DFT. • The HOMO and LUMO orbitals were predicted from the calculations.

  15. Synthesis, structure, and photoluminescent properties of metal-organic coordination polymers assembled with bithiophenedicarboxylic acid. (United States)

    Zhao, Jiao; Wang, Xiu-Li; Shi, Xin; Yang, Qi-Hua; Li, Can


    Four novel metal-organic coordination polymers with the formulas Mn(3)(btdc)(3)(DMF)(4) (1), Co(btdc)(DMF)(3) (2), Zn(btdc)(DMF)(3) (3), and Zn(btdc)(4,4'-bpy)(0.5) (4), where H(2)btdc = 2,2'-bithiophene-5,5'-dicarboxylic acid, DMF = N,N'-dimethylformamide, and 4,4'-bpy = 4,4'-bipyridine, have been successfully synthesized. Crystal 1 with Mn(2+) as the cation features a three-dimensional (3D) infinite framework built from trimanganese clusters, and crystals 2 and 3 with Co(2+) and Zn(2+), respectively, as the cation both have one-dimensional zigzag polymeric coordination chains. Crystal 4 synthesized using a mixture of 4,4'-bpy and H(2)btdc exhibits a triply interpenetrating 3D framework built from a dizinc paddlewheel second building unit with a distorted primitive cubic single net. The results of UV/vis spectra indicate that metal binding does not disturb the detailed electronic structure of the ligand. We also demonstrate that Zn(2+) can greatly enhance the luminescence emission of the H(2)btdc ligand, and the emission intensity of crystal 4 is almost 20 times higher than that of the free H(2)btdc ligand. Steady-state and time-resolved spectroscopic measurement reveal that the more rigid environment of the btdc ligand can stabilize the highly excited long-lived states in metal-organic frameworks (MOFs), which thus greatly changes the emission properties of MOFs.

  16. Synthesis and characterization of the europium (III) complex as an organic luminescent material

    Energy Technology Data Exchange (ETDEWEB)

    Zhuo Zuliang; Zhang Fujun; Xu Zheng; Lu Lifang; Li Junming; Wang Yongsheng [Key Laboratory of Luminescence and Optical Information (Beijing Jiaotong University), Ministry of Education, Beijing 100044 (China); Lv Yuguang, E-mail: [The Provincial Key Laboratory of Biomaterials, College of Chemistry and Pharmacy, Jiamusi University, Jiamusi 154007 (China)


    The red emission organic material Eu(coumarin){sub 3{center_dot}}2H{sub 2}O complex was synthesized and its morphology, energy level alignment and luminescence characteristics were studied by using scanning electron microscopy, Fourier transform infrared spectra, cyclic voltammetry and ultraviolet-visible absorption spectra and fluorescence spectra. Eu(coumarin){sub 3{center_dot}}2H{sub 2}O shows bright red emission originating from Eu{sup 3+} ions under 345 nm light excitation. The luminescence lifetime of Eu{sup 3+} in this complex is about 580 {mu}s. To improve the quality of Eu(coumarin){sub 3{center_dot}}2H{sub 2}O thin films, Eu(coumarin){sub 3{center_dot}}2H{sub 2}O was doped with a poly(N-vinylcarbazole) (PVK) solution. The organic materials 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP) and aluminum quinoline (Alq{sub 3}) were used as hole-blocking and electron-transporting layers in our fabricated electroluminescence (EL) devices on indium tin oxide (ITO) substrates, respectively. The EL devices ITO/poly-(3,4-ethylenedioxythiophene):poly-(styrenesulphonic acid) (PEDOT:PSS)/emitting layer (PVK:Eu)/BCP/Alq{sub 3}/Al were fabricated, and EL spectra were measured under different driving voltages. There is one emission peaking at 490 nm in addition to the characteristic emission peaks of Eu{sup 3+}, which should be attributed to the spectral overlap between the PVK emission and electroplex emission originating from PVK and BCP interfaces. This explanation can be positively supported by the dependence of the EL spectral variation of ITO/ PVK/BCP/Alq{sub 3}/Al devices on the driving voltage.

  17. Design and Synthesis of Organic Small Molecules for Industrial and Biomedical Technology Nanomaterial Augmentation (United States)

    Chapman, James Vincent, III

    Organic chemistry used to augment nanoparticles and nanotubes, as well as more traditional materials, is a subject of great interest across multiple fields of applied chemistry. Herein we present an example of both nanoparticle and nanotube augmentation with organic small molecules to achieve an enhanced or otherwise infeasible application. The first chapter discusses the modification of two different types of Microbial Fuel Cell (MFC) anode brush bristle fibers with positive surface charge increasing moieties to increase quantitative bacterial adhesion to these bristle fibers, and therefore overall MFC electrogenicity. Type-1 brush bristles, comprised of polyacrylonitrile, were modified via the electrostatic attachment of 1-pyrenemethylamine hydrochloride. Type-2 brush bristles, comprised of nylon, were modified via the covalent attachment of ethylenediamine. Both modified brush types were immersed in an E. Coli broth for 1 hour, stained with SYTORTM 9 Green Fluorescent Nucleic Acid Stain from ThermoFisher Scientific (SYTO-9), and examined under a Biotek Citation 3 fluorescent microscope to visually assess differences in bacterial adherence. In both trials, a clear increase in amount of bacterial adhesion to the modified bristles was observed over that of the control. The second chapter demonstrates a potential biomedical technology application wherein a polymerizable carbocyanine-type dye was synthesized and bound to a chitosan backbone to produce a water-soluble photothermal nanoparticle. Laser stimulation of both free and NP-conjugated aqueous solutions of the carbocyanine dye with Near-Infrared (NIR) Spectrum Radiation showed an increase in temperature directly correlated with the concentration of the dye which was more pronounced in the free particle solutions.

  18. Facile synthesis and characterization of trimesic acid-Cu based metal organic frameworks (United States)

    Sahiner, Nurettin; Sel, Kivanc; Ozturk, Omer Faruk; Demirci, Sahin; Terzi, Gozde


    Metal-organic frameworks based on trimesic acid (TMA) as organic linker and Cu (II) as metal ions from different metal salts such as CuCl2, Cu(NO3)2, CuSO4 and Cu(CH3COOH)2 were prepared in relatively environmentally friendly media e.g., at room temperature in DI water and at the boiling point of ethanol. The prepared TMA-Cu MOFs showed very interesting porosity and optical coloring based on the source of the used metal salts and preparation medium. The prepared MOFs were characterized in terms of their porosity with BET measurements and it was found that about 850 m2/g for the MOF prepared from Cu(NO3)2 salt in ethanol. The amounts of metal ions connected to TMA were determined by atomic absorption spectroscopy measurements (AAS) after dissolution of TMA-Cu MOFs by concentrated HCl treatments. From AAS measurements the mole ratio of Cu(II) to TMA was found to vary between 1.5 and 2, depending on the source of metal ions and the solvent used during preparation. The structural analysis and thermal characterization of the prepared MOFs were done by using FT-IR and TGA analysis, respectively. Additionally, TMA-Cu based MOF disks were prepared and their conductivities were determined by I-V measurements. The conductivity of TMA-Cu MOFs was calculated to be between 8.26E-08 and 5.29E-11 S/cm.

  19. Current perspectives in proteomic analysis of abiotic stress in Grapevines

    Directory of Open Access Journals (Sweden)

    Iniga Seraphina George


    Full Text Available Grapes are an important crop plant which forms the basis of a globally important industry. Grape and wine production is particularly vulnerable to environmental and climatic fluctuations, which makes it essential for us to develop a greater understanding of the molecular level responses of grape plants to various abiotic stresses. The completion of the initial grape genome sequence in 2007 has led to a significant increase in research on grapes using proteomics approaches. In this article, we discuss some of the current research on abiotic stress in grapevines, in the context of abiotic stress research in other plant species. We also highlight some of the current limitations in grapevine proteomics and identify areas with promising scope for potential future research.

  20. A spray-drying strategy for synthesis of nanoscale metal-organic frameworks and their assembly into hollow superstructures (United States)

    Carné-Sánchez, Arnau; Imaz, Inhar; Cano-Sarabia, Mary; Maspoch, Daniel


    Metal-organic frameworks (MOFs) are among the most attractive porous materials known today. Their miniaturization to the nanoscale—into nanoMOFs—is expected to serve myriad applications from drug delivery to membranes, to open up novel avenues to more traditional storage and catalysis applications, and to enable the creation of sophisticated superstructures. Here, we report the use of spray-drying as a versatile methodology to assemble nanoMOFs, yielding spherical hollow superstructures with diameters smaller than 5 µm. This strategy conceptually mimics the emulsions used by chemists to confine the synthesis of materials, but does not require secondary immiscible solvents or surfactants. We demonstrate that the resulting spherical, hollow superstructures can be processed into stable colloids, whose disassembly by sonication affords discrete, homogeneous nanoMOFs. This spray-drying strategy enables the construction of multicomponent MOF superstructures, and the encapsulation of guest species within these superstructures. We anticipate that this will provide new routes to capsules, reactors and composite materials.

  1. Diurnal Profiles of Melatonin Synthesis-Related Indoles, Catecholamines and Their Metabolites in the Duck Pineal Organ

    Directory of Open Access Journals (Sweden)

    Bogdan Lewczuk


    Full Text Available This study characterizes the diurnal profiles of ten melatonin synthesis-related indoles, the quantitative relations between these compounds, and daily variations in the contents of catecholamines and their metabolites in the domestic duck pineal organ. Fourteen-week-old birds, which were reared under a 12L:12D cycle, were killed at two-hour intervals. The indole contents were measured using HPLC with fluorescence detection, whereas the levels of catecholamines and their metabolites were measured using HPLC with electrochemical detection. All indole contents, except for tryptophan, showed significant diurnal variations. The 5-hydroxytryptophan level was approximately two-fold higher during the scotophase than during the photophase. The serotonin content increased during the first half of the photophase, remained elevated for approximately 10 h and then rapidly decreased in the middle of the scotophase. N-acetylserotonin showed the most prominent changes, with a more than 15-fold increase at night. The melatonin cycle demonstrated only an approximately 5-fold difference between the peak and nadir. The 5-methoxytryptamine content was markedly elevated during the scotophase. The 5-hydroxyindole acetic acid, 5-hydroxytryptophol, 5-methoxyindole acetic acid and 5-methoxytryptophol profiles were analogous to the serotonin rhythm. The norepinephrine and dopamine contents showed no significant changes. The DOPA, DOPAC and homovanillic acid levels were higher during the scotophase than during the photophase. Vanillylmandelic acid showed the opposite rhythm, with an elevated level during the daytime.

  2. A terpene synthase is involved in the synthesis of the volatile organic compound sodorifen of Serratia plymuthica 4Rx13

    Directory of Open Access Journals (Sweden)

    Dajana eDomik


    Full Text Available Bacteria release a plethora of volatile organic compounds (VOCs, including compounds with extraordinary structures. Sodorifen (IUPAC name: 1,2,4,5,6,7,8-heptamethyl-3-methylenebicyclo[3.2.1]oct-6-ene is a recently identified and unusual volatile hydrocarbon that is emitted by the rhizobacterium Serratia plymuthica 4Rx13. Sodorifen comprises a bicyclic ring structure solely consisting of carbon and hydrogen atoms, where every carbon atom of the skeleton is substituted with either a methyl or a methylene group. This unusual feature of sodorifen made a prediction of its biosynthetic origin very difficult and so far its biosynthesis was unknown. To unravel the biosynthetic pathway we performed genome and transcriptome analyses to identify candidate genes. One knockout mutant (SOD_c20750 showed the desired negative sodorifen phenotype. Here it was shown for the first time that this gene is indispensable for the synthesis of sodorifen and strongly supports the hypothesis that sodorifen descends from the terpene metabolism. SOD_c20750 is the first bacterial terpene cyclase isolated from Serratia spp. and Enterobacteriales. Homology modeling revealed a 3D structure, which indicated a functional role of amino acids for intermediate cation stabilization (W325 and putative proton acceptance (Y331. Moreover, the size and hydrophobicity of the active site strongly indicated that indeed the enzyme may catalyze the unusual compound sodorifen.

  3. Diurnal profiles of melatonin synthesis-related indoles, catecholamines and their metabolites in the duck pineal organ. (United States)

    Lewczuk, Bogdan; Ziółkowska, Natalia; Prusik, Magdalena; Przybylska-Gornowicz, Barbara


    This study characterizes the diurnal profiles of ten melatonin synthesis-related indoles, the quantitative relations between these compounds, and daily variations in the contents of catecholamines and their metabolites in the domestic duck pineal organ. Fourteen-week-old birds, which were reared under a 12L:12D cycle, were killed at two-hour intervals. The indole contents were measured using HPLC with fluorescence detection, whereas the levels of catecholamines and their metabolites were measured using HPLC with electrochemical detection. All indole contents, except for tryptophan, showed significant diurnal variations. The 5-hydroxytryptophan level was approximately two-fold higher during the scotophase than during the photophase. The serotonin content increased during the first half of the photophase, remained elevated for approximately 10 h and then rapidly decreased in the middle of the scotophase. N-acetylserotonin showed the most prominent changes, with a more than 15-fold increase at night. The melatonin cycle demonstrated only an approximately 5-fold difference between the peak and nadir. The 5-methoxytryptamine content was markedly elevated during the scotophase. The 5-hydroxyindole acetic acid, 5-hydroxytryptophol, 5-methoxyindole acetic acid and 5-methoxytryptophol profiles were analogous to the serotonin rhythm. The norepinephrine and dopamine contents showed no significant changes. The DOPA, DOPAC and homovanillic acid levels were higher during the scotophase than during the photophase. Vanillylmandelic acid showed the opposite rhythm, with an elevated level during the daytime.

  4. Synthesis of nanomagnetic fluids and their UV spectrophotometric response with aliphatic organic acids and 1st tier dendrimers (United States)

    Pandya, Shivani R.; Singh, Man


    Synthesis of Magnetic nanoparticles were made using coprecipitation method on mixing Fe+3 and Fe+2 in 2:1 ratio with aqueous 8M NaOH which on heating at 90°C for 2 h has yielded 85% magnetic (Fe3O4) nanoparticles (MNPs), characterized by XRD, VSM, SEM, and HR-TEM. The formic acid (FA), oxalic acid (OA) and citric acid (CA), the series of aliphatic organic acids along with Trimesoyl 1, 3, 5 tridimethyl malonate (TTDMM), trimesoyl 1, 3, 5 tridiethyl malonate (TTDEM), trimesoyl 1, 3, 5 tridipropyl malonate (TTDPM), trimesoyl 1, 3, 5 tridibutyl malonate (TTDBM) and trimesoyl 1, 3, 5 tridihexyl malonate (TTDHM) 1st tier dendrimers were used separately for preparing nanomagnetic fluid. From 25 to 150 µM MNPs at an interval of 25 µM were dispersed in 150 µM of acids and dendrimers separately with DMSO. UV-VIS spectrophotometry showed a maximum MNPs dispersion with TTDMM against others and found to be most stable nanomagnetic fluid on account of capping type mechanism of acids.

  5. Diurnal Profiles of Melatonin Synthesis-Related Indoles, Catecholamines and Their Metabolites in the Duck Pineal Organ (United States)

    Lewczuk, Bogdan; Ziółkowska, Natalia; Prusik, Magdalena; Przybylska-Gornowicz, Barbara


    This study characterizes the diurnal profiles of ten melatonin synthesis-related indoles, the quantitative relations between these compounds, and daily variations in the contents of catecholamines and their metabolites in the domestic duck pineal organ. Fourteen-week-old birds, which were reared under a 12L:12D cycle, were killed at two-hour intervals. The indole contents were measured using HPLC with fluorescence detection, whereas the levels of catecholamines and their metabolites were measured using HPLC with electrochemical detection. All indole contents, except for tryptophan, showed significant diurnal variations. The 5-hydroxytryptophan level was approximately two-fold higher during the scotophase than during the photophase. The serotonin content increased during the first half of the photophase, remained elevated for approximately 10 h and then rapidly decreased in the middle of the scotophase. N-acetylserotonin showed the most prominent changes, with a more than 15-fold increase at night. The melatonin cycle demonstrated only an approximately 5-fold difference between the peak and nadir. The 5-methoxytryptamine content was markedly elevated during the scotophase. The 5-hydroxyindole acetic acid, 5-hydroxytryptophol, 5-methoxyindole acetic acid and 5-methoxytryptophol profiles were analogous to the serotonin rhythm. The norepinephrine and dopamine contents showed no significant changes. The DOPA, DOPAC and homovanillic acid levels were higher during the scotophase than during the photophase. Vanillylmandelic acid showed the opposite rhythm, with an elevated level during the daytime. PMID:25032843

  6. Facile synthesis and enhanced photocatalytic activity of single-crystalline nanohybrids for the removal of organic pollutants (United States)

    Pervaiz, Erum; Liu, Honghong; Yang, Minghui


    This study focused on the synthesis of α-MoO3/rGO (rGO, reduced graphene oxide). One-dimensional nanohybrids under mild conditions and a low temperature wet chemical route produced highly pure single-crystalline orthorhombic α-MoO3 on GO sheets. Four nanohybrids, labeled as GMO-0, GMO-1, GMO-2 and GMO-3, were synthesized with different mass chargings of GO (0 mg, 40 mg, 60 mg and 100 mg, respectively). The photocatalytic performance for reduction of organic pollutants was analyzed. The presence of different amounts of GO in the prepared metal oxide hybrids altered the performance of the material as elaborated by the Brunauer-Emmett-Teller surface area, UV-visible diffuse reflectance spectra and the resulting reduction of organic dyes depicted by photocatalytic experiments. GO as a support material and active co-catalyst decreased the band gap of α-MoO3 (2.82 eV) to lower values (2.51 eV), rendering the prepared hybrids usable for visible-light-induced photocatalysis. The large specific surface area (72 m2 g-1) of the mesoporous α-MoO3/rGO nanohybrid made it an efficient photocatalyst for the elimination of azo dyes. Very fast reduction (100%) of Rhodamine B was observed in a few minutes, while Congo Red was degraded by 76% in 10 min, leading to the formation of stable intermediates that were completely neutralized in 12-14 h under light irradiation. The amount of GO loaded in the samples was limited to a point to achieve better results. After that, increasing the amount of GO decreased the extent of degradation due to the presence of a higher electron acceptor. Photocatalytic experiments revealed the synergistic effect, high selectivity of the prepared nanohybrids and degradation of azo dyes. The kinetics of the degradation reaction were studied and found to follow a pseudo first-order reaction.

  7. Polyfluorinated substances in abiotic standard reference materials

    NARCIS (Netherlands)

    Reiner, J.L.; Blaine, A.C.; Higgins, C.P.; Kwadijk, C.J.A.F.


    The National Institute of Standards and Technology (NIST) has a wide range of Standard Reference Materials (SRMs) which have values assigned for legacy organic pollutants and toxic elements. Existing SRMs serve as homogenous materials that can be used for method development, method validation, and

  8. Synthesis and binding properties of arylethyne-linked porphyrin-zinc complexes for organic electronics applications. (United States)

    Reainthippayasakul, W; Paosawatyanyong, B; Bhanthumnavin, W


    Conjugated meso-alkynyl 5,15-dimesitylporphyrin metal complexes have been synthesized by Sonogashira coupling reaction in good yields. Alkynyl groups were chosen as a link at the meso positions in order to extend the pi-conjugated length of porphyrin rings. These synthesized porphyrin derivatives were characterized by 1H NMR spectroscopy and MALDI-TOF mass spectrometry. Moreover, UV-visible spectroscopy and fluorescence spectroscopy were also used to investigate their photophysical properties. It has been demonstrated that central metal ions as well as meso substituents on porphyrin rings affected the electronic absorption and emission spectra of the compounds. Spectroscopic results revealed that alkyne-linked porphyrin metal complexes showed higher pi-conjugation compared with porphyrin building blocks resulting in red shifts in both absorption and emission spectra. Coordination properties of synthesized porphyrins were preliminarily investigated by UV-visible absorption and fluorescence emission spectroscopic titration with pyridine as axial ligand. The formation of porphyrin-pyridine complexes resulted in significant red shifts in absorption spectra and decrease of fluorescence intensity in emission spectra. Moreover, the 1H NMR titration experiments suggested that central metal ions play an important role to coordinate with pyridine and the coordination of porphyrin zinc(II) complex with pyridine occur in a 1:1 ratio. From these spectroscopic results, alkyne-linked porphyrin metal complexes offer potential applications as materials for optical organic nanosensors.

  9. Synthesis, characterization and heterogeneous base catalysis of amino functionalized lanthanide metal-organic frameworks (United States)

    Huang, Jinping; Li, Chunmei; Tao, Lingling; Zhu, Huilin; Hu, Gang


    Lanthanide metal-organic frameworks (Ln-MOFs) are featured by their tolerance to water and dense structure. In this work, an amine-functionalized Ln-MOF was facilely synthesized by coordination of terbium with 2-aminoterephthalic acid under the condition of microwave irradiation. The crystal structure was characterized by single crystal X-ray diffraction, FT-IR, Raman, TG-DTA and XPS analysis. The basic catalytic activity of the NH2-Tb-MOF was evaluated for Knoevenagel condensation and Henry reactions. Apart from the high activity and 100% selectivity to the condensation product, the NH2-Tb-MOF catalyst could be easily recycled and reused owing to the high stability of the MOF framework formed by coordination of Tb3+ with carboxylic groups. Remarkably, the NH2-Tb-MOF exhibited size-selective catalysis to substrates. For the small-sized reactants, it displayed comparable activity to the homogeneous catalyst of aniline owing to the high dispersion of NH2- active sites and the low diffusion limits. However, in the same reaction system, extremely poor activity in Knoevenagel condensation and Henry reaction for the bulky substrate 4-(tert-butyl) benzaldehyde was observed due to the both effects of substitute and inhibition of diffusion into the micropores. Crystal structure analysis provided a mechanistic evidence that the heterogeneous base catalysis arose from the amino groups densely distributed inside the micropores.

  10. Graphene-Templated Synthesis of Magnetic Metal Organic Framework Nanocomposites for Selective Enrichment of Biomolecules. (United States)

    Cheng, Gong; Wang, Zhi-Gang; Denagamage, Sachira; Zheng, Si-Yang


    Successful control of homogeneous and complete coating of graphene or graphene-based composites with well-defined metal organic framework (MOF) layers is a great challenge. Herein, novel magnetic graphene MOF composites were constructed via a simple strategy for self-assembly of well-distributed, dense, and highly porous MOFs on both sides of graphene nanosheets. Graphene functionalized with magnetic nanoparticles and carboxylic groups on both sides was explored as the backbone and template to direct the controllable self-assembly of MOFs. The prepared composite materials have a relatively high specific surface area (345.4 m(2) g(-1)), and their average pore size is measured to be 3.2 nm. Their relatively high saturation magnetization (23.8 emu g(-1)) indicates their strong magnetism at room temperature. Moreover, the multifunctional composite was demonstrated to be a highly effective affinity material in selective extraction and separation of low-concentration biomolecules from biological samples, in virtue of the size-selection property of the unique porous structure and the excellent affinity of the composite materials. Besides providing a solution for the construction of well-defined functional graphene-based MOFs, this work could also contribute to selective extraction of biomolecules, in virtue of the universal affinity between immobilized metal ions and biomolecules.

  11. Synthesis, characterization and electrochemical investigations of mixed-ligand copper(II)-organic supramolecular frameworks (United States)

    Singh, Sandeep K.; Srivastava, Ashish Kumar; Srivastava, Krishna; Banerjee, Rahul; Prasad, Jagdish


    Two mixed-ligand copper(II)-organic coordination compounds with 5,5‧-dimethyl-2,2‧-bipyridine (5,5‧-Me2bpy) as a primary ligand while aliphatic malonate (Hmal) and aromatic 2-hydroxynicotinate (2-OHNA) as secondary ligands, were synthesized. These complexes are formulated as: [Cu(Hmal)(5,5‧-Me2bpy)(H2O)](ClO4) 1 and [Cu2(2-OHNA)2(5,5‧-Me2bpy)2(NO3)](NO3) 2. These two complexes were structurally characterized by single crystal X-ray diffraction analysis. Characterization was further supported by powder X-ray diffraction analysis, elemental analyses, FT-IR, FAB-MASS and TGA, DSC studies. Cyclic voltammetric and UV-visible spectral studies of these two complexes have also been done. The electrochemical studies of complex 1 in DMSO and DMF have shown that this complex undergoes quasi-reversible diffusion-controlled one-electron transfer reaction without any chemical complication while complex 2 in DMSO undergoes quasi-reversible diffusion-controlled one electron transfer reaction, following EC mechanism. The electrochemical behaviour of complex 2 in DMF is complicated probably due to presence of more than one species in solution phase.

  12. Synthesis, functionalisation and post-synthetic modification of bismuth metal-organic frameworks. (United States)

    Köppen, M; Beyer, O; Wuttke, S; Lüning, U; Stock, N


    Two new bismuth metal-organic frameworks (Bi-MOFs) were discovered using high throughput experiments employing bismuth(iii) nitrate pentahydrate and triazine-2,4,6-triyl-tribenzoic acid (H 3 TATB). The reaction was carried out for long reaction times (∼5 d) in a water/DMF-mixture and resulted in the formation of [Bi 2 (O)(OH)(TATB)]·H 2 O (denoted as CAU-35). By switching to short reaction times and a methanol/DMF-mixture as the solvent, an analogue of CAU-7-BTB with the composition [Bi(TATB)]·DMF·6H 2 O (denoted as CAU-7-TATB) was obtained. The use of the amino-functionalised H 3 TATB linker (H 3 TATB-NH 2 ) resulted in the formation of a functionalised porous Bi-MOF with the composition [Bi(TATB-NH 2 )]·5H 2 O·0.5DMF (CAU-7-TATB-NH 2 ). The structures of CAU-35 and CAU-7-TATB were successfully solved and refined from the PXRD data. CAU-7-TATB-NH 2 was post-synthetically modified using anhydrides (acetic anhydride and valeric anhydride), cyclic anhydrides (succinic anhydride and phthalic anhydride), and 1,3-propane sultone. The degree of conversion ranged from 33% to 79%.

  13. Facile synthesis of glucoamylase embedded metal-organic frameworks (glucoamylase-MOF) with enhanced stability. (United States)

    Nadar, Shamraja S; Rathod, Virendra K


    The self-assembled glucoamylase metal-organic framework (glucoamylase-MOF) was synthesized by facile one-step method within 20min by simply mixing aqueous solution of 2-methylimidazole (160mM), glucoamylase (5mg/mL) and zinc acetate (40mM) at room temperature (28±2°C). The prepared glucoamylase-MOF was characterized by using FT-IR, confocal scanning laser microscopy, XRD and SEM. The robustness and thermal stability of glucoamylase embedded MOF was evaluated in terms of half-life (in the range of 60-80°C) which showed 6 folds increment as against free form. Further, in Michaelis-Menten kinetics studies, glucoamylase entrapped MOF exhibited higher K m value and lower V max value as compared to native enzyme. Moreover, the immobilized glucoamylase exhibited up to 57% of residual activity after six consecutive cycles of reuse, whereas it retained 91% of residual activity till 25days of storage. Finally, the conformational changes occurred after the encapsulation of glucoamylase in the interior of MOF, which was analyzed by using FT-IR data analysis tools. Copyright © 2016 Elsevier B.V. All rights reserved.

  14. Low-temperature synthesis of carbon nanotubes on indium tin oxide electrodes for organic solar cells. (United States)

    Capasso, Andrea; Salamandra, Luigi; Di Carlo, Aldo; Bell, John Marcus; Motta, Nunzio


    The electrical performance of indium tin oxide (ITO) coated glass was improved by including a controlled layer of carbon nanotubes directly on top of the ITO film. Multiwall carbon nanotubes (MWCNTs) were synthesized by chemical vapor deposition, using ultrathin Fe layers as catalyst. The process parameters (temperature, gas flow and duration) were carefully refined to obtain the appropriate size and density of MWCNTs with a minimum decrease of the light harvesting in the cell. When used as anodes for organic solar cells based on poly(3-hexylthiophene) (P3HT) and phenyl-C61-butyric acid methyl ester (PCBM), the MWCNT-enhanced electrodes are found to improve the charge-carrier extraction from the photoactive blend, thanks to the additional percolation paths provided by the CNTs. The work function of as-modified ITO surfaces was measured by the Kelvin probe method to be 4.95 eV, resulting in an improved matching to the highest occupied molecular orbital level of the P3HT. This is in turn expected to increase the hole transport and collection at the anode, contributing to the significant increase of current density and open-circuit voltage observed in test cells created with such MWCNT-enhanced electrodes.

  15. Low-temperature synthesis of carbon nanotubes on indium tin oxide electrodes for organic solar cells

    Directory of Open Access Journals (Sweden)

    Andrea Capasso


    Full Text Available The electrical performance of indium tin oxide (ITO coated glass was improved by including a controlled layer of carbon nanotubes directly on top of the ITO film. Multiwall carbon nanotubes (MWCNTs were synthesized by chemical vapor deposition, using ultrathin Fe layers as catalyst. The process parameters (temperature, gas flow and duration were carefully refined to obtain the appropriate size and density of MWCNTs with a minimum decrease of the light harvesting in the cell. When used as anodes for organic solar cells based on poly(3-hexylthiophene (P3HT and phenyl-C61-butyric acid methyl ester (PCBM, the MWCNT-enhanced electrodes are found to improve the charge-carrier extraction from the photoactive blend, thanks to the additional percolation paths provided by the CNTs. The work function of as-modified ITO surfaces was measured by the Kelvin probe method to be 4.95 eV, resulting in an improved matching to the highest occupied molecular orbital level of the P3HT. This is in turn expected to increase the hole transport and collection at the anode, contributing to the significant increase of current density and open-circuit voltage observed in test cells created with such MWCNT-enhanced electrodes.


    Directory of Open Access Journals (Sweden)

    Teguh Hari Sucipto


    Full Text Available The human immunodeficiency virus (HIV is viruses known as rotaviruses. Potential target for therapeutic is reverse transcriptase (RT, possesses an RNA dependent DNA polymerase, DNA-dependent DNA polymerase and ribonuclease H fuctions. Imidazoles have high anti-HIV inhibitory activity, some derivates of imidazole reported drugs. 8-chloro-2,3-dihydroimidazole[1,2-b] [1,4,2]benzodithiazine-5,5-dioxides and 9-chloro-2,3,4-trihydropyri-mido[1,2-b][1,4,2]benzodithi-azine-6,6-dioxides. This compounds succesfully identified anti-HIV activity. Copper is a bio-essential element and copper complexes have been extensively utilized in metal mediated DNA cleavage for the generation of activated oxygen species. It has been reported that teraaza macrocyclic copper coordination compounds have anti-HIV activities. Studies have shown that these macrocyclic complexes can react with DNA in different binding fashions and exhibit effective nuclease activities. Complex compounds are compounds in which there is an atom that acts as the central atom and trotter group of molecules that can be either neutral or charged ions. Application a metal-organic (complex compounds, especially copper metal and derivates of imidazole. So, in this study can explore new anti-HIV candidate.

  17. Solvents in Organic Synthesis: Replacement and Multi-step Reaction Systems

    DEFF Research Database (Denmark)

    Gani, Rafiqul; Gómez, Paola Arenas; Folic, Milica


    Solvents are widely used as reaction media in the chemical, fine chemical and pharmaceutical industries, but they present numerous environmental, health and safety (EHS) challenges that need to be managed and are subject to increasing regulatory scrutiny. The above issues, together with the princ......Solvents are widely used as reaction media in the chemical, fine chemical and pharmaceutical industries, but they present numerous environmental, health and safety (EHS) challenges that need to be managed and are subject to increasing regulatory scrutiny. The above issues, together...... 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......- and solvent-related properties that directly or indirectly influence a given reaction. In this work, the methodology has been extended through its application to several cases of increased process complexity involving multi-step reaction systems and solvent substitution for specific reaction steps in existing...

  18. Modular and Stepwise Synthesis of a Hybrid Metal-Organic Framework for Efficient Electrocatalytic Oxygen Evolution. (United States)

    Shen, Jian-Qiang; Liao, Pei-Qin; Zhou, Dong-Dong; He, Chun-Ting; Wu, Jun-Xi; Zhang, Wei-Xiong; Zhang, Jie-Peng; Chen, Xiao-Ming


    The paddle-wheel type cluster Co2(RCOO)4(LT)2 (R = substituent group, LT = terminal ligand), possessing unusual metal coordination geometry compared with other cobalt compounds, may display high catalytic activity but is highly unstable especially in water. Here, we show that with judicious considerations of the host/guest geometries and modular synthetic strategies, the labile dicobalt clusters can be immobilized and stabilized in a metal-organic framework (MOF) as coordinative guests. The Fe(na)4(LT) fragment in the MOF [{Fe3(μ3-O)(bdc)3}4{Fe(na)4(LT)}3] (H2bdc = 1,4-benzenedicaboxylic acid, Hna = nicotinic acid) can be removed to give [{Fe3(μ3-O)(bdc)3}4] with a unique framework connectivity possessing suitable distribution of open metal sites for binding the dicobalt cluster in the form of Co2(na)4(LT)2. After two-step, single-crystal to single-crystal, postsynthetic modifications, a thermal-, water-, and alkaline-stable MOF [{Fe3(μ3-O)(bdc)3}4{Co2(na)4(LT)2}3] containing the desired dicobalt cluster was obtained, giving extraordinarily high electrocatalytic oxygen evolution activity in water at pH = 13 with overpotential as low as 225 mV at 10.0 mA cm-2.

  19. Enzymatic synthesis of a sucrose-containing linear polyester in nearly anhydrous organic media. (United States)

    Patil, D R; Rethwisch, D G; Dordick, J S


    A variety of enzymes have been found to acylate sucrose in anhydrous pyridine. The enzymic reaction is highly selective; with trifluoroethylbutyrate as ester donor, enzyme-catalyzed transesterification of sucrose yielded sucrose 1'-butyrate and sucrose 6, 1'-dibutyrate. No sucrose-tributyrates were formed. Using a similar technique, a long-chain linear sucrose polyester has been prepared using Proleather, an alkaline protease from a Bacillus sp. This protease catalyzes the esterification of sucrose with bis(2, 2, 2-trifluoroethyladipate) in a 1:1 ratio to yield a sucrose-containing polyester with M(w) = 2100 and M(n) = 1600 for a polydispersity of 1. 31. Polymers with molecular weights in excess of 13, 000 have been prepared by this enzymic approach, indicating that molecules containing over 30 sucrose units have been produced. The polyester is extremely water soluble and soluble in polar organic solvents. As with the sucrose dibutyrate, the polyester has ester linkages at the C6 and C1' positions on the sucrose. The polyester can be depolymerized using Proleather in aqueous buffer, pH7. After 9 days in aqueous buffer, Proleather catalyzed the breakdown of the polyester to an M(w) of ca. 900. This sucrose-containing polyester may have applications as a water-absorbent, biodegradable plastic for use as diapers and hygienic products, water-treatment chemicals, and components of drug delivery systems.

  20. Synthesis, crystal structure and luminescent properties of a new samarium-fluorescein metal-organic framework (United States)

    Thomas, Jesty; Ambili, K. S.


    A new metal-organic framework with empirical formula C43H30NO12Sm was solvothermally synthesized using SmCl3, fluorescein and N, N-Dimethyl formamide (DMF) and characterized by single crystal X-ray diffraction, powder X-ray diffraction, infrared spectroscopy, UV-Visible spectroscopy, scanning electron microscopy, optical microscopy, photoluminescence spectroscopy, CHN elemental analysis and thermogravimetric analysis. Single crystal X-ray diffraction revealed that the crystal structure belongs to the triclinic system, P-1 space group with a = 12.113 (6) Å, b = 12.1734 (7) Å, c = 13.2760(8) Å, α = 67.930(3)⁰, β = 87.779(3)⁰, γ = 77.603(3)⁰ and V = 1769.71 (17) Å3. The photoluminescence spectrum showed emission peaks at 550 nm, 600 nm and 647 nm due to the characteristic transitions 4G5/2 to 6H5/2, 4G5/2 to 6H7/2 and 4G5/2 to 6H9/2 respectively, when excited at 398 nm.

  1. Total synthesis of the cyclopeptide alkaloid abyssenine A. Application of inter- and intramolecular copper-mediated coupling reactions in organic synthesis. (United States)

    Toumi, Mathieu; Couty, François; Evano, Gwilherm


    The first total synthesis of the 15-membered ring cyclopeptide alkaloid abyssenine A 1 has been achieved with a longest linear sequence of 15 steps. Central to the synthetic approach was an efficient copper-mediated Ullmann coupling/Claisen rearrangement sequence allowing for both ipso and ortho functionalization of aromatic iodide 4. This sequence was used for the synthesis of the aromatic core. The synthetic utility of copper-catalyzed coupling reactions was further demonstrated to install the enamide with a concomitant straightforward macrocyclization starting from acyclic alpha-amido-omega-vinyl iodide 13.

  2. An ribonuclease T2 family protein modulates Acinetobacter baumannii abiotic surface colonization.

    Directory of Open Access Journals (Sweden)

    Anna C Jacobs

    Full Text Available Acinetobacter baumannii is an emerging bacterial pathogen of considerable medical concern. The organism's transmission and ability to cause disease has been associated with its propensity to colonize and form biofilms on abiotic surfaces in health care settings. To better understand the genetic determinants that affect biomaterial attachment, we performed a transposon mutagenesis analysis of abiotic surface-colonization using A. baumannii strain 98-37-09. Disruption of an RNase T2 family gene was found to limit the organism's ability to colonize polystyrene, polypropylene, glass, and stainless steel surfaces. DNA microarray analyses revealed that in comparison to wild type and complemented cells, the RNase T2 family mutant exhibited reduced expression of 29 genes, 15 of which are predicted to be associated with bacterial attachment and surface-associated motility. Motility assays confirmed that RNase T2 mutant displays a severe motility defect. Taken together, our results indicate that the RNase T2 family protein identified in this study is a positive regulator of A. baumannii's ability to colonize inanimate surfaces and motility. Moreover, the enzyme may be an effective target for the intervention of biomaterial colonization, and consequently limit the organism's transmission within the hospital setting.

  3. Mechanism for the Coupled Photochemistry of Ammonia and Acetylene: Implications for Giant Planets, Comets and Interstellar Organic Synthesis (United States)

    Keane, Thomas C.


    Laboratory studies provide a fundamental understanding of photochemical processes in planetary atmospheres. Photochemical reactions taking place on giant planets like Jupiter and possibly comets and the interstellar medium are the subject of this research. Reaction pathways are proposed for the coupled photochemistry of NH3 (ammonia) and C2H2 (acetylene) within the context Jupiter's atmosphere. We then extend the discussion to the Great Red Spot, Extra-Solar Giant Planets, Comets and Interstellar Organic Synthesis. Reaction rates in the form of quantum yields were measured for the decomposition of reactants and the formation of products and stable intermediates: HCN (hydrogen cyanide), CH3CN (acetonitrile), CH3CH = N-N = CHCH3 (acetaldazine), CH3CH = N-NH2 (acetaldehyde hydrazone), C2H5NH2 (ethylamine), CH3NH2 (methylamine) and C2H4 (ethene) in the photolysis of NH3/C2H2 mixtures. Some of these compounds, formed in our investigation of pathways for HCN synthesis, were not encountered previously in observational, theoretical or laboratory photochemical studies. The quantum yields obtained allowed for the formulation of a reaction mechanism that attempts to explain the observed results under varying experimental conditions. In general, the results of this work are consistent with the initial observations of Ferris and Ishikawa (1988). However, their proposed reaction pathway which centers on the photolysis of CH3CH = N-N = CHCH3 does not explain all of the results obtained in this study. The formation of CH3CH = N-N = CHCH3 by a radical combination reaction of CH3CH = N• was shown in this work to be inconsistent with other experiments where the CH3CH = N• radical is thought to form but where no CH3CH = N-N = CHCH3 was detected. The importance of the role of H atom abstraction reactions was demonstrated and an alternative pathway for CH3CH = N-N = CHCH3 formation involving nucleophilic reaction between N2H4 and CH3CH = NH is advanced.

  4. Mechanism for the Coupled Photochemistry of Ammonia and Acetylene: Implications for Giant Planets, Comets and Interstellar Organic Synthesis. (United States)

    Keane, Thomas C


    Laboratory studies provide a fundamental understanding of photochemical processes in planetary atmospheres. Photochemical reactions taking place on giant planets like Jupiter and possibly comets and the interstellar medium are the subject of this research. Reaction pathways are proposed for the coupled photochemistry of NH3 (ammonia) and C2H2 (acetylene) within the context Jupiter's atmosphere. We then extend the discussion to the Great Red Spot, Extra-Solar Giant Planets, Comets and Interstellar Organic Synthesis. Reaction rates in the form of quantum yields were measured for the decomposition of reactants and the formation of products and stable intermediates: HCN (hydrogen cyanide), CH3CN (acetonitrile), CH3CH = N-N = CHCH3 (acetaldazine), CH3CH = N-NH2 (acetaldehyde hydrazone), C2H5NH2 (ethylamine), CH3NH2 (methylamine) and C2H4 (ethene) in the photolysis of NH3/C2H2 mixtures. Some of these compounds, formed in our investigation of pathways for HCN synthesis, were not encountered previously in observational, theoretical or laboratory photochemical studies. The quantum yields obtained allowed for the formulation of a reaction mechanism that attempts to explain the observed results under varying experimental conditions. In general, the results of this work are consistent with the initial observations of Ferris and Ishikawa (1988). However, their proposed reaction pathway which centers on the photolysis of CH3CH = N-N = CHCH3 does not explain all of the results obtained in this study. The formation of CH3CH = N-N = CHCH3 by a radical combination reaction of CH3CH = N• was shown in this work to be inconsistent with other experiments where the CH3CH = N• radical is thought to form but where no CH3CH = N-N = CHCH3 was detected. The importance of the role of H atom abstraction reactions was demonstrated and an alternative pathway for CH3CH = N-N = CHCH3 formation involving nucleophilic reaction between N2H4 and CH3CH = NH is advanced.

  5. Synthesis, growth and characterization of π conjugated organic nonlinear optical chalcone derivative

    Energy Technology Data Exchange (ETDEWEB)

    Prabhu, A.N., E-mail: [Department of Physics, Manipal Institute of Technology, Manipal University, Manipal 576 104 (India); Upadhyaya, V. [Department of Physics, Manipal Institute of Technology, Manipal University, Manipal 576 104 (India); Jayarama, A., E-mail: [Department of Physics, Mangalore Institute of Technology and Engineering (MITE), Moodabidri 574225 (India); Subrahmanya Bhat, K. [Department of Chemistry, Manipal Institute of Technology, Manipal University, Manipal 576 104 (India)


    A new potentially useful nonlinear optical organic material, 1-(5-chlorothiophen-2-yl)-3-(2,3-dimethoxyphenyl)prop-2-en-1-one, has been synthesized and grown as a high-quality single crystal by the slow evaporation technique. The grown crystals were characterized by FT-IR, NMR, thermal analysis, and UV–visible spectroscopy. The material is thermally stabile up to 111 °C. The mechanical property of the grown crystals was studied using Vickers microhardness tester and the load dependence hardness was observed. The third order nonlinear optical properties of the material such as real and imaginary part of χ{sup (3)}, nonlinear absorption coefficient and nonlinear refractive index were determined using nanosecond laser pulses at 532 nm wavelength by employing Z-scan technique. The nonlinear refractive index is found to be of the order of 10{sup −11} cm{sup 2} W{sup −1}. The magnitude of third order susceptibility is of the order of 10{sup −13} esu. The observed increase in the third order nonlinearity in these molecules clearly indicates the electronic origin. The compounds exhibit good optical limiting at 532 nm. The best optical limiting behavior of this molecule is due to the substituted strong electron donor. - Highlights: ► A novel thiophene substituted NLO crystal has been grown using methanol as solvent. ► The crystals were characterized by using FTIR, TGA/DTA and UV–visible spectroscopy. ► The n{sub 2} and χ{sup (3)} values is of the order of 10{sup −11} cm{sup 2} W{sup −1} and 10{sup −13} esu respectively. ► The crystals show better optical limiting behavior.

  6. Two novel metal–organic coordination polymers based on diphosphonate and oxalate: Synthesis, structures and properties

    Energy Technology Data Exchange (ETDEWEB)

    Niu, Qing-Jun; Zheng, Yue-Qing, E-mail:; Zhou, Lin-Xia; Zhu, Hong-Lin


    Two 2-(1-imidazole)-1-hydroxyl-1,1'-ethylidenediphosphonato and oxalic acid bridged coordination polymers (H{sub 2}en)[Co{sub 3}(H{sub 2}zdn){sub 2}(ox)(H{sub 2}O){sub 2}] (1) and Cd{sub 2}(H{sub 2}zdn)(ox){sub 0.5}(H{sub 2}O) (2) (2-(1-imidazole)-1-hydroxyl-1,1'-ethylidenediphosphonic acid=H{sub 5}zdn; oxalic acid=H{sub 2}ox) were synthesized under hydrothermal conditions and characterized by the infrared (IR), thermogravimetric analyses (TGA), elemental analyses (EA) and X-ray diffraction (XRD). Compound 1 is bridged by phosphonate anions to 1D chain, and further linked by oxalate anions to 2D layer. Compound 2 is bridged by O–P–O units of H{sub 5}zdn to the layer, and then pillared by oxalate anions to generate 3D frameworks. Compound 1 shows anti-ferromagnetic behaviors analyzed with the temperature-dependent zero-field ac magnetic susceptibilities, while compound 2 exhibits an influence on the luminescent property. - Graphical abstract: Linked by oxalate, two zoledronate-based metal–organic frameworks are synthesized, which exhibits the different frameworks. Magnetism and luminescent properties have been studied. The weak antiferromagnetic coupling is conducted in 1. - Highlights: • Compound 1 and 2 are first linked by oxalate anion based on zoledronic acid. • Compound 1 generates a classic “dia Diamond” (6{sup 6}) topology. • Compound 2 exhibits a (4{sup 4}·6{sup 2})(4{sup 4}·6{sup 6}) topology. • Magnetism and luminescent properties of 1 and 2 have been studied, respectively.

  7. Hydrothermal synthesis and structural characterization of metal-organic frameworks based on new tetradentate ligands. (United States)

    Liang, Yue; Yuan, Wei-Guan; Zhang, Shu-Fang; He, Zhan; Xue, Junru; Zhang, Xia; Jing, Lin-Hai; Qin, Da-Bin


    The hydrothermal reaction of two new tetradentate ligands with different metal salts of cadmium nitrate, zinc chloride, cobalt nitrate and deprotonated terephthalic acid (H2tp), isophthalic acid (H2ip), 4,4'-oxybisbenzoic acid (H2obba) in H2O/DMF or H2O/methanol gave three metal-organic frameworks (MOFs): {[Zn2(L1)(tp)(formate)2]·H2O}n (), {[Cd2(L2)(ip)2]·2H2O}n (), {[Co2(L2)(obba)2]}n () (L1 = 1,2-bis {2,6-bis [(1H-imidazol-1-yl) methyl]-4-methylphenoxy} ethane, L2 = 1,3-bis {2,6-bis [(1H-imidazol-1-yl) methyl]-4-methylphenoxy} propane). The structures of the frameworks are established by single-crystal X-ray diffraction. Compound is a three-dimensional (3D) framework with a 2-fold interpenetrated form, which exhibits a 2-nodal (3,4)-connected fsh-3,4-P21/c net with a {8(3)}2{8(5)·10} topology. Compound has a 2-nodal (4,8)-connected 3D framework where the dinuclear cadmium cluster secondary building units (SBUs) assemble with isophthalate and ligand L2 to construct a rare topological type sqc22 net with a {3(2)·5(4)}{3(4)·4(4)·5(10)·6(10)} topology. Whereas, Compound can be extended to a 2D interlocked (4,4)-connected 4,4 L28 net with the point symbol {4·6(4)·8}2{4(2)·6(4)}. L1 and L2 are tetradentate ligands with diverse linkers and display different coordination modes. In addition, the thermal stability and photochemical properties of the frameworks are also investigated.

  8. Synthesis and characterization of fluorinated azadipyrromethene complexes as acceptors for organic photovoltaics

    Directory of Open Access Journals (Sweden)

    Forrest S. Etheridge


    Full Text Available Homoleptic zinc(II complexes of di(phenylacetyleneazadipyrromethene (e.g., Zn(WS32 are potential non-fullerene electron acceptors for organic photovoltaics. To tune their properties, fluorination of Zn(WS32 at various positions was investigated. Three fluorinated azadipyrromethene-based ligands were synthesized with fluorine at the para-position of the proximal and distal phenyl groups, and at the pyrrolic phenylacetylene moieties. Additionally, a CF3 moiety was added to the pyrrolic phenyl positions to study the effects of a stronger electron withdrawing unit at that position. The four ligands were chelated with zinc(II and BF2+ and the optical and electrochemical properties were studied. Fluorination had little effect on the optical properties of both the zinc(II and BF2+ complexes, with λmax in solution around 755 nm and 785 nm, and high molar absorptivities of 100 × 103 M−1cm−1 and 50 × 103 M−1cm−1, respectively. Fluorination of Zn(WS32 raised the oxidation potentials by 0.04 V to 0.10 V, and the reduction potentials by 0.01 V to 0.10 V, depending on the position and type of substitution. The largest change was observed for fluorine substitution at the proximal phenyl groups and CF3 substitution at the pyrrolic phenylacetylene moieties. The later complexes are expected to be stronger electron acceptors than Zn(WS32, and may enable charge transfer from other conjugated polymer donors that have lower energy levels than poly(3-hexylthiophene (P3HT.

  9. One-pot synthesis of core-expanded naphthalene diimides: enabling N-substituent modulation for diverse n-type organic materials. (United States)

    Hu, Yunbin; Qin, Yunke; Gao, Xike; Zhang, Fengjiao; Di, Chong-an; Zhao, Zheng; Li, Hongxiang; Zhu, Daoben


    A mild and versatile one-pot synthesis of core-expanded naphthalene diimides has been developed, which undergoes a nucleophilic aromatic substitution reaction and then an imidization reaction, allowing an easy and low-cost access to diverse n-type organic materials. Some newly synthesized compounds by this one-pot operation exhibited high electron mobility of up to 0.70 cm(2) V(-1) s(-1) in ambient conditions. © 2011 American Chemical Society

  10. Synthesis, structures, and luminescent and magnetic properties of Ln-Ag heterometal-organic frameworks. (United States)

    Zhao, Xiao-Qing; Zhao, Bin; Wei, Shi; Cheng, Peng


    A series of Ln-Ag heterometal-organic frameworks based on 4-hydroxylpyridine-2,6-dicarboxylic acid (H(3)CAM) with formulas {LaAg(2)(CAM)(HCAM)(H(2)O)(2)}(n) (1), {LnAg(HCAM)(2)(H(2)O)(3)}(n) (Ln = Pr, 2; Nd, 3; Sm, 4; Eu, 5), and {LnAg(3)(CAM)(2)(H(2)O)}(n) (Ln = Gd, 6; Tb, 7; Dy, 8; Tm, 9; Yb, 10), have been synthesized with the hydrothermal reaction of Ln(OH)(3), Ag(2)O, and H(3)CAM at 160 degrees C. The single-crystal X-ray diffraction analyses reveal that three kinds of structures are exclusively governed by the size of lanthanide ions and the progression of structures is mainly ascribed to the lanthanide contraction effect. Compound 1 consists of a 3D network with an alpha-polonium-like Ag(+)-homometallic net and helical La(3+) chain. Compounds 2-5 display a 2D honeycomb-like structure with 18-membered Ln(3)Ag(3)O(12) motifs, and compounds 6-10 can be described as a sandwich-like 3D framework built of a 3D Ag(+)-homometallic net and 2D Ln(3+)-4(4) layer. In 4 (Sm), 5 (Eu), 7 (Tb), and 8 (Dy) samples, the efficient energy transfer from CAM to Ln(III) ions was observed, which results in the typical intense emissions of corresponding Ln(III) ions in the visible region, and the strongest emissions are (4)G(5/2) --> (6)H(7/2) (602 nm), (5)D(0) --> (7)F(2) (614 nm), (5)D(4) --> (7)F(5) (548 nm), and (4)F(9/2) --> (6)H(13/2) (576 nm) transitions. Variable-temperature magnetic susceptibility measurements of 6-10 show that the ferromagnetic interaction between gadolinium(III) ions appears in 6, whereas the mu(eff) values of 7-10 smoothly decrease on cooling. For the orbital contribution of Ln(III) ions, it is very difficult to determine the intrinsic magnetic interactions between Ln(III) ions.

  11. Aging changes of macromolecular synthesis in the digestive organs of mice as revealed by microscopic radioautography and X-ray microanalysis

    Energy Technology Data Exchange (ETDEWEB)

    Nagata, Tetsuji [Shinshu Univ., Matsumoto (Japan). School of Medicine. Dept. of Anatomy and Cell Biology]. E-mail:


    For the purpose of elucidating the aging changes of macromolecular synthesis such as DNA, RNA, proteins, glycoproteins, glycides and lipids in various organ systems of experimental animals, we have studied the digestive organs of aging mice and rats as a series of systematic studies using light and electron microscopic radioautography after incorporations with macromolecular precursors. The experimental animals mainly used were ddY strain mice at various aging groups from embryo to postnatal days 1 and 3, weeks 1 and 2, months 1, 2, 6, 12 up to 2 year senescent stages as well as several groups of adult Wistar rats. The animals were injected with such macromolecular precursors as {sup 3}H - thymidine for DNA, {sup 3}H-uridine for RNA, {sup 3}H-leucine and {sup 3}H proline for proteins, {sup 35}SO{sub 4} for glycoproteins, {sup 3} H-glucosamine for glucides and {sup 3}H-glycerol for lipids. The results demonstrated that these precursors were incorporated into various cell types in the oral cavity, the salivary glands, the esophagus, the stomach, the small and large intestines, the liver and the pancreas at various ages from perinatal to juvenile, mature and senescent stages, showing specific patterns of macromolecular synthesis. It is concluded that these specific patterns of macromolecular synthesis in respective cell types demonstrated the organ specificity of aging of animals. (author)

  12. Molecular Cloning and Characterization of Galactinol Synthases in Camellia sinensis with Different Responses to Biotic and Abiotic Stressors. (United States)

    Zhou, Yu; Liu, Yan; Wang, Shuangshuang; Shi, Cong; Zhang, Ran; Rao, Jia; Wang, Xu; Gu, Xungang; Wang, Yunsheng; Li, Daxiang; Wei, Chaoling


    Galactinol synthase (GolS) is a key biocatalyst for the synthesis of raffinose family oligosaccharides (RFOs). RFOs accumulation plays a critical role in abiotic stress adaptation, but the relationship between expression of GolS genes and biotic stress adaptation remains unclear. In this study, two CsGolS genes were found to be highly up-regulated in a transcriptome library of Ectropic oblique-attacked Camellia sinensis. Three complete CsGolS genes were then cloned and characterized. Gene transcriptional analyses under biotic and abiotic stress conditions indicated that the CsGolS1 gene was sensitive to water deficit, low temperature, and abscisic acid, while CsGolS2 and CsGolS3 genes were sensitive to pest attack and phytohormones. The gene regulation and RFOs determination results indicated that CsGolS1 was primarily related to abiotic stress and CsGolS2 and CsGolS3 were related to biotic stress. GolS-mediated biotic stress adaptations have not been studied in depth, so further analysis of this new biological function is required.

  13. RNA:protein ratio of the unicellular organism as a characteristic of phosphorous and nitrogen stoichiometry and of the cellular requirement of ribosomes for protein synthesis

    Directory of Open Access Journals (Sweden)

    Sams Carl E


    Full Text Available Abstract Background Mean phosphorous:nitrogen (P:N ratios and relationships of P:N ratios with the growth rate of organisms indicate a surprising similarity among and within microbial species, plants, and insect herbivores. To reveal the cellular mechanisms underling this similarity, the macromolecular composition of seven microorganisms and the effect of specific growth rate (SGR on RNA:protein ratio, the number of ribosomes, and peptide elongation rate (PER were analyzed under different conditions of exponential growth. Results It was found that P:N ratios calculated from RNA and protein contents in these particular organisms were in the same range as the mean ratios reported for diverse organisms and had similar positive relationships with growth rate, consistent with the growth-rate hypothesis. The efficiency of protein synthesis in microorganisms is estimated as the number of active ribosomes required for the incorporation of one amino acid into the synthesized protein. This parameter is calculated as the SGR:PER ratio. Experimental and theoretical evidence indicated that the requirement of ribosomes for protein synthesis is proportional to the RNA:protein ratio. The constant of proportionality had the same values for all organisms, and was derived mechanistically from the characteristics of the protein-synthesis machinery of the cell (the number of nucleotides per ribosome, the average masses of nucleotides and amino acids, the fraction of ribosomal RNA in the total RNA, and the fraction of active ribosomes. Impairment of the growth conditions decreased the RNA:protein ratio and increased the overall efficiency of protein synthesis in the microorganisms. Conclusion Our results suggest that the decrease in RNA:protein and estimated P:N ratios with decrease in the growth rate of the microorganism is a consequence of an increased overall efficiency of protein synthesis in the cell resulting from activation of the general stress response and

  14. Temporal abiotic variability structures invertebrate communities in agricultural drainage ditches

    NARCIS (Netherlands)

    Whatley, M.H.; Vonk, J.A.; van der Geest, H.G.; Admiraal, W.


    Abiotic variability is known to structure lotic invertebrate communities, yet its influence on lentic invertebrates is not clear. This study tests the hypothesis that variability of nutrients and macro-ions are structuring invertebrate communities in agricultural drainage ditches. This was


    NARCIS (Netherlands)

    Wahl, Martin; Jormalainen, Veijo; Eriksson, Britas Klemens; Coyer, James A.; Molis, Markus; Schubert, Hendrik; Dethier, Megan; Karez, Rolf; Kruse, Inken; Lenz, Mark; Pearson, Gareth; Rohde, Sven; Wikstrom, Sofia A.; Olsen, Jeanine L.; Lesser, M


    Stress regimes defined as the synchronous or sequential action of abiotic and biotic stresses determine the performance and distribution of species. The natural patterns of stress to which species are more or less well adapted have recently started to shift and alter under the influence of global

  16. Effect of biotic and abiotic factors on composition and foraging ...

    African Journals Online (AJOL)

    Elucidating the influence of ecological factors on composition and foraging intensity of subterranean termites is critical in development of sustainable termite management strategies. Our aim was therefore to analyze the effect of selected biotic and abiotic factors on composition and foraging intensity of termites. We used ...

  17. Current trends in genetic manipulations to enhance abiotic and ...

    African Journals Online (AJOL)

    Success in breeding for better adapted varieties to abiotic and biotic stresses depends on the concerted efforts of various research domains including plant and cell physiology, molecular biology, genetics and breeding. However, such process is time consuming. The production of transgenic plants by genetic engineering ...

  18. Genetic adaptability of inheritance of resistance to biotic and abiotic ...

    African Journals Online (AJOL)

    Moreover, generation means analysis of several traits assessed in diverse environmental conditions revealed that the mode of inheritance of each trait varied with the biotic or abiotic stress level. With less stress level, only additive and dominance effects was found significant. In contrast with moderate and higher stress level ...

  19. Effect of plant growth hormones and abiotic stresses on germination ...

    African Journals Online (AJOL)

    Phosphatases are widely found in plants having intracellular and extracellular activities. Phosphatases are believed to be important for phosphorous scavenging and remobilization in plants, but its role in adaptation to abiotic stresses and growth hormones at germination level has not been critically evaluated. To address ...

  20. Understanding the Posttranscriptional Regulation of Plant Responses to Abiotic Stress

    KAUST Repository

    AlShareef, Sahar A.


    Constitutive and alternative splicing of pre-mRNAs from multiexonic genes controls the diversity of the proteome; these precisely regulated processes also fine-tune responses to cues related to growth, development, and biotic and abiotic stresses. Recent work showed that AS is pervasive across plant species, with more than 60% of intron-containing genes producing different isoforms. Mammalian cell-based assays have discovered various AS small-molecule inhibitors that perturb splicing and thereby provide invaluable tools for use as chemical probes to uncover the molecular underpinnings of splicing regulation and as potential anticancer compounds. Here, I show that the macrolide Pladienolide B (PB) and herboxidiene (GEX1A) inhibits both constitutive and alternative splicing, mimics an abiotic stress signal, and activates the abscisic acid (ABA) pathway in plants. Moreover, PB and GEX1A activate genome-wide transcriptional patterns involved in abiotic stress responses in plants. PB and GEX1A treatment triggered the ABA signaling pathway, activated ABA-inducible promoters, and led to stomatal closure. Interestingly, PB and GEX1A elicited similar cellular changes, including alterations in the patterns of transcription and splicing, suggesting that these compounds might target the same spliceosome complex in plant cells. This work establishes PB and GEX1A as potent splicing inhibitors in plants that can be used to probe the assembly, dynamics, and molecular functions of the spliceosome and to study the interplay between splicing stress and abiotic stresses, as well as having potential biotechnological applications.