Abiotic Condensation Synthesis of Glyceride Lipids and Wax Esters Under Simulated Hydrothermal Conditions

NASA Astrophysics Data System (ADS)

Rushdi, Ahmed I.; Simoneit, Bernd R. T.

2006-04-01

Precursor compounds for abiotic proto cellular membranes are necessary for the origin of life. Amphipathic compounds such as fatty acids and acyl glycerols are important candidates for micelle/bilayer/vesicle formation. Two sets of experiments were conducted to study dehydration reactions of model lipid precursors in aqueous media to form acyl polyols and wax esters, and to evaluate the stability and reactions of the products at elevated temperatures. In the first set, mixtures of n-nonadecanoic acid and ethylene glycol in water, with and without oxalic acid, were heated at discrete temperatures from 150 ∘C to 300 ∘C for 72 h. The products were typically alkyl alkanoates, ethylene glycolyl alkanoates, ethylene glycolyl bis-alkanoates and alkanols. The condensation products had maximum yields between 150 ∘C and 250 ∘C, and were detectable and thus stable under hydrothermal conditions to temperatures < 300 ∘C. In the second set of experiments, mixtures of n-heptanoic acid and glycerol were heated using the same experimental conditions, with and without oxalic acid, between 100 ∘C and 250 ∘C. The main condensation products were two isomers each of monoacylglycerols and diacylglycerols at all temperatures, as well as minor amounts of the fatty acid anhydride and methyl ester. The yield of glyceryl monoheptanoates generally increased with increasing temperature and glyceryl diheptanoates decreased noticeably with increasing temperature. The results indicate that condensation reactions and abiotic synthesis of organic lipid compounds under hydrothermal conditions occur easily, provided precursor concentrations are sufficiently high.

Abiotic condensation synthesis of glyceride lipids and wax esters under simulated hydrothermal conditions.

PubMed

Rushdi, Ahmed I; Simoneit, Bernd R T

2006-04-01

Precursor compounds for abiotic proto cellular membranes are necessary for the origin of life. Amphipathic compounds such as fatty acids and acyl glycerols are important candidates for micelle/bilayer/vesicle formation. Two sets of experiments were conducted to study dehydration reactions of model lipid precursors in aqueous media to form acyl polyols and wax esters, and to evaluate the stability and reactions of the products at elevated temperatures. In the first set, mixtures of n-nonadecanoic acid and ethylene glycol in water, with and without oxalic acid, were heated at discrete temperatures from 150 ( composite function)C to 300 ( composite function)C for 72 h. The products were typically alkyl alkanoates, ethylene glycolyl alkanoates, ethylene glycolyl bis-alkanoates and alkanols. The condensation products had maximum yields between 150 ( composite function)C and 250 ( composite function)C, and were detectable and thus stable under hydrothermal conditions to temperatures < 300 ( composite function)C. In the second set of experiments, mixtures of n-heptanoic acid and glycerol were heated using the same experimental conditions, with and without oxalic acid, between 100 ( composite function)C and 250 ( composite function)C. The main condensation products were two isomers each of monoacylglycerols and diacylglycerols at all temperatures, as well as minor amounts of the fatty acid anhydride and methyl ester. The yield of glyceryl monoheptanoates generally increased with increasing temperature and glyceryl diheptanoates decreased noticeably with increasing temperature. The results indicate that condensation reactions and abiotic synthesis of organic lipid compounds under hydrothermal conditions occur easily, provided precursor concentrations are sufficiently high.

Abiotic Synthesis of Nucleic Acids: Hypochromicity and Future Research

NASA Technical Reports Server (NTRS)

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

2017-01-01

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.

MICROWAVES IN ORGANIC SYNTHESIS

EPA Science Inventory

The effect of microwaves, a non-ionizing radiation, on organic reactions is described both in polar solvents and under solvent-free conditions. The special applications are highlighted in the context of solventless organic synthesis which involve microwave (MW) exposure of neat r...

Nanostructured Interfaces for Organized Mesoscopic Biotic-Abiotic Materials

DTIC Science & Technology

2011-09-30

stratified films. Bio-assisted and surface-mediated growth of inorganic nanoparticles . The use of biomolecules as templates for the synthesis of...multi-length scale morphologies of several selected inorganic materials including bi-metal nanoparticles (Au-Ag, Au-Pd) as well as TiO2, ZnO nanodots...polyaminoacid-decorated surfaces which serve for both nucleation and growth of uniformly distributed gold nanoparticles at ambient conditions. We found that

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

NASA Astrophysics Data System (ADS)

Gonzalez, Julia; Peña, Jasquelin

2016-04-01

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

Protein synthesis inhibition activity by strawberry tissue protein extracts during plant life cycle and under biotic and abiotic stresses.

PubMed

Polito, Letizia; Bortolotti, Massimo; Mercatelli, Daniele; Mancuso, Rossella; Baruzzi, Gianluca; Faedi, Walther; Bolognesi, Andrea

2013-07-25

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

Experimental and Thermodynamic Constraints on Serpentinization: Implications for Fluid Chemistry, Abiotic Synthesis of Hydrocarbons, and Subsurface Microbial Processes

NASA Astrophysics Data System (ADS)

McCollom, T. M.

2005-12-01

Serpentinized rocks have received a great deal of attention in recent years, primarily because they are believed to play significant roles in supporting autotrophic, hydrogen-based microbial communities and in the abiotic synthesis of methane and other organic compounds. Both of these processes are a consequence of the high H2 concentrations generated by reaction of water with ultramafic rocks during serpentinization. The amount of H2 produced during serpentinization is dependent on both thermodynamic and kinetic constraints, which can be evaluated through numerical thermodynamic models and laboratory experiments. Because olivine is thermodynamically stable at temperatures above ~375°C, alteration of ultramafic rocks at higher temperatures generates only minor amounts of H2. Even at lower temperatures olivine may equilibrate with the fluid after only partial reaction, so that olivine may persist stably in partially serpentinized rocks. Olivine only becomes completely unstable at ~315°C, so that the maximum potential for H2 production only occurs at or below this temperature. At high temperatures, serpentinization proceeds rapidly, so that thermodynamic constraints provide the primary control on H2 production. However, the rate of serpentinization becomes sufficiently slow below ~150°C that the residence of time of fluids may prevent high concentrations of H2 from accumulating. Since H2 generation during serpentinization is primarily attributable to conversion of ferrous Fe in olivine to ferric Fe in magnetite, another factor that may limit H2 production is the sequestration of ferrous Fe in brucite or serpentine. Some serpentines and brucites are reported to contain significant amounts of Fe, but these data are somewhat uncertain because the analyses may include microcrystalline magnetite. Although the thermodynamic properties of solid solutions of these minerals are highly uncertain, the available data suggest that the Fe content of serpentines and brucite may

Induction of glutathione synthesis and glutathione reductase activity by abiotic stresses in maize and wheat.

PubMed

Kocsy, Gábor; Szalai, Gabriella; Galiba, Gábor

2002-06-21

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.

Electrifying Organic Synthesis.

PubMed

Wiebe, Anton; Gieshoff, Tile; Möhle, Sabine; Rodrigo, Eduardo; Zirbes, Michael; Waldvogel, Siegfried R

2018-05-14

The direct synthetic organic use of electricity is currently experiencing a renaissance. More synthetically oriented laboratories working in this area are exploiting both novel and more traditional concepts, paving the way to broader applications of this niche technology. As only electrons serve as reagents, the generation of reagent waste is efficiently avoided. Moreover, stoichiometric reagents can be regenerated and allow a transformation to be conducted in an electrocatalytic fashion. However, the application of electroorganic transformations is more than minimizing the waste footprint, it rather gives rise to inherently safe processes, reduces the number of steps of many syntheses, allows for milder reaction conditions, provides alternative means to access desired structural entities, and creates intellectual property (IP) space. When the electricity originates from renewable resources, this surplus might be directly employed as a terminal oxidizing or reducing agent, providing an ultra-sustainable and therefore highly attractive technique. This Review surveys recent developments in electrochemical synthesis that will influence the future of this area. © 2018 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

Organization and Regulation of Soybean SUMOylation System under Abiotic Stress Conditions

PubMed Central

Li, Yanjun; Wang, Guixin; Xu, Zeqian; Li, Jing; Sun, Mengwei; Guo, Jingsong; Ji, Wei

2017-01-01

Covalent attachment of the small ubiquitin-related modifier, SUMO, to substrate proteins plays a significant role in plants under stress conditions, which can alter target proteins' function, location, and protein-protein interactions. Despite this importance, information about SUMOylation in the major legume crop, soybean, remains obscure. In this study, we performed a bioinformatics analysis of the entire soybean genome and identified 40 genes belonged to six families involved in a cascade of enzymatic reactions in soybean SUMOylation system. The cis-acting elements analysis revealed that promoters of SUMO pathway genes contained different combinations of stress and development-related cis-regulatory elements. RNA-seq data analysis showed that SUMO pathway components exhibited versatile tissue-specific expression patterns, indicating coordinated functioning during plant growth and development. qRT-PCR analysis of 13 SUMO pathway members indicated that majority of the SUMO pathway members were transcriptionally up-regulated by NaCl, heat and ABA stimuli during the 24 h period of treatment. Furthermore, SUMOylation dynamics in soybean roots under abiotic stress treatment were analyzed by western blot, which were characterized by regulation of SUMOylated proteins. Collectively, this study defined the organization of the soybean SUMOylation system and implied an essential function for SUMOylation in soybean abiotic stress responses. PMID:28878795

Analysis of Cell Wall-Related Genes in Organs of Medicago sativa L. under Different Abiotic Stresses.

PubMed

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

2015-07-16

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.

Analysis of Cell Wall-Related Genes in Organs of Medicago sativa L. under Different Abiotic Stresses

PubMed Central

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

2015-01-01

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. PMID:26193255

Evidence for abiotic sulfurization of marine dissolved organic matter in sulfidic environments

NASA Astrophysics Data System (ADS)

Pohlabeln, A. M.; Niggemann, J.; Dittmar, T.

2016-02-01

Sedimentary organic matter abiotically sulfurizes in sulfidic marine environments. Here we hypothesize that sulfurization also affects dissolved organic matter (DOM), and that sulfidic marine environments are sources of dissolved organic sulfur (DOS) to the ocean. To test these hypotheses we studied solid-phase extractable (SPE) DOS in the Black Sea at various water column depths (oxic and anoxic) and in sediment porewaters from the German Wadden Sea. The concentration and molecular composition of SPE-DOS from these sites and from the oxic water columns of the North Sea (Germany) and of the North Pacific were compared. In support of our hypotheses, SPE-DOS concentrations were elevated in sulfidic waters compared to oxic waters. For a detailed molecular characterization of SPE-DOS, selective wet-chemical alteration experiments targeting different sulfur-containing functional groups were applied prior to Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR-MS). These experiments included harsh hydrolysis, selective derivatization of thiols, oxidation, and deoxygenation to test for thioesters, sulfonic acid esters, alkylsulfates, thiols, non-aromatic thioethers, and sulfoxides. Additionally, collision-induced fragmentation experiments were applied to test for sulfonic acids. The tests revealed that the sulfonic acid group was the main structural feature in SPE-DOS, independent of the environmental conditions of the sampling site. Only in Wadden Sea anoxic porewater also non-aromatic thioethers were found which are presumably not stable in oxic waters. The findings from our field studies were confirmed in laboratory experiments, where we abiotically sulfurized marine and algal-derived DOM under conditions similar to that in anoxic marine sediments.

Salt lakes of Western Australia - Natural abiotic formation of volatile organic compounds

NASA Astrophysics Data System (ADS)

Krause, T.; Studenroth, S.; Mulder, I.; Tubbesing, C.; Kotte, K.; Ofner, J.; Junkermann, W.; Schöler, H. F.

2012-04-01

Western Australia is a semi-/arid region that is heavily influenced by global climate change and agricultural land use. The area is known for its many ephemeral saline and hypersaline lakes with a wide range of hydrogeochemical parameters that have gradually changed over the last fifty years. Historically, the region was covered by eucalyptus trees and shrubs, but was cleared mainly within 10 years after WWII to make room for wheat and live stock. After the clearance of the deep rooted native plants the groundwater started to rise, bringing increased amounts of dissolved salts and minerals to the surface and discharging them into streams and lakes. Thus most of Western Australia is influenced by secondary salinisation (soil salting) [1]. Another problem is that the discharged minerals affect the pH of ground and surface water, which ranges from acidic to slightly basic. During the 2011 campaign surface water was measured with a pH between 2.5 and 7.1. Another phenomenon in Western Australia is the decrease of rainfall over the last decades assumed to be linked to the secondary salinisation. The rising saline and mineral rich groundwater increases the biotical and abiotical activity of the salt lakes. Halogenated and non-halogenated volatile organic compounds emitted from those lakes undergo fast oxidation and chemical reactions to form small particles modifying cloud microphysics and thus suppressing rain events [2]. Our objective is to gain a better understanding of this extreme environment with its hypersaline acidic lakes with regard to the potential abiotic formation of volatile organic compounds and its impact on the local climate. In spring 2011 fifty-three sediment samples from ten salt lakes in the Lake King region where taken, freeze-dried and ground. In order to simulate the abiotic formation of volatile organic compounds the soil samples were resuspended with water in gas-tight headspace vials. The headspace was measured using a purge and trap GC

Biotic and abiotic controls on biogenic volatile organic compound fluxes from a subalpine forest floor

NASA Astrophysics Data System (ADS)

Gray, Christopher M.; Monson, Russell K.; Fierer, Noah

2014-04-01

Nonmethane biogenic volatile organic compounds (BVOCs) play key roles in the atmosphere, where they can influence a wide range of chemical processes, and in soils, where they can alter the rates of biogeochemical cycles and impact the growth of plants and soil organisms. However, the diversity and quantities of BVOCs released from or taken up by soils remain poorly characterized as do the biotic and abiotic controls on these fluxes. Here we used proton transfer reaction mass spectrometry to quantify BVOC flux rates from soils with and without active root systems in a subalpine coniferous forest. The total measured BVOC flux averaged 102 nmol m-2 h-1 (an estimated 2.0 µg-C m-2 h-1). The individual BVOCs with the highest net emissions from soil included monoterpenes and methanol (averaging 646 and 641 ng-C m-2 h-1, respectively) while soil represented a net sink of isoprene (-98 ng-C m-2 h-1) and formaldehyde (-37 ng-C m-2 h-1). Tree roots, directly or indirectly, contributed an average of 53% of the total carbon emitted from the soil as BVOCs, with methanol and acetaldehyde among those BVOCs most strongly associated with active root presence. The fluxes of most of the dominant BVOCs emitted from soil, including methanol, increased linearly with increasing temperature. Together the fluxes of certain BVOCs into or out of the forest floor (particularly methanol, isoprene, and monoterpenes) are likely relevant to ecosystem-level processes and belowground ecology, but these fluxes are highly variable and are strongly controlled by both root presence and soil abiotic conditions.

Persistent Organic Pollutants in Biotic and Abiotic Components of Antarctic Pristine Environment

NASA Astrophysics Data System (ADS)

Bhardwaj, Laxmikant; Chauhan, Abhishek; Ranjan, Anuj; Jindal, Tanu

2018-02-01

Over the past decades, research in Antarctica has built a new understanding of Antarctica, its past, present and future. Human activities and long-range pollutants are increasing on the Antarctic continent. Research on persistent organic pollutants (POPs) has been carried out internationally by several countries having their permanent research stations to explain the impact of an ever increasing range of POPs in Antarctic ecosystem. POPs have been detected in Antarctica despite its geographical isolation and almost complete absence of human settlements. The presence of POPs in different abiotic (atmosphere, water bodies, sediments, soil, sea ice) and biotic components (mosses, lichens, krill, penguins, skua, etc.) in Antarctica has been studied and documented around for decades and has either been banned or strictly regulated but is still found in the environment. This review focuses on recent research pertaining to sources and occurrence of POPs in Antarctic lake water, soil, sediment, lichen, mosses and other Antarctic marine community. This review also proposes to summarize the current state of research on POPs in Antarctica environment and draw the earliest conclusions on possible significance of POPs in Antarctica based on presently available information from related Antarctic environment.

Persistent Organic Pollutants in Biotic and Abiotic Components of Antarctic Pristine Environment

NASA Astrophysics Data System (ADS)

Bhardwaj, Laxmikant; Chauhan, Abhishek; Ranjan, Anuj; Jindal, Tanu

2018-05-01

Over the past decades, research in Antarctica has built a new understanding of Antarctica, its past, present and future. Human activities and long-range pollutants are increasing on the Antarctic continent. Research on persistent organic pollutants (POPs) has been carried out internationally by several countries having their permanent research stations to explain the impact of an ever increasing range of POPs in Antarctic ecosystem. POPs have been detected in Antarctica despite its geographical isolation and almost complete absence of human settlements. The presence of POPs in different abiotic (atmosphere, water bodies, sediments, soil, sea ice) and biotic components (mosses, lichens, krill, penguins, skua, etc.) in Antarctica has been studied and documented around for decades and has either been banned or strictly regulated but is still found in the environment. This review focuses on recent research pertaining to sources and occurrence of POPs in Antarctic lake water, soil, sediment, lichen, mosses and other Antarctic marine community. This review also proposes to summarize the current state of research on POPs in Antarctica environment and draw the earliest conclusions on possible significance of POPs in Antarctica based on presently available information from related Antarctic environment.

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

EPA Science Inventory

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...

Indenylmetal Catalysis in Organic Synthesis.

PubMed

Trost, Barry M; Ryan, Michael C

2017-03-06

Synthetic organic chemists have a long-standing appreciation for transition metal cyclopentadienyl complexes, of which many have been used as catalysts for organic transformations. Much less well known are the contributions of the benzo-fused relative of the cyclopentadienyl ligand, the indenyl ligand, whose unique properties have in many cases imparted differential reactivity in catalytic processes toward the synthesis of small molecules. In this Review, we present examples of indenylmetal complexes in catalysis and compare their reactivity to their cyclopentadienyl analogues, wherever possible. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

PubMed

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

2017-03-01

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 GA 3 (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 GA 3 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 GA 3 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 GA 3 elicited synthesis of L-proline in berries, and mono- and sesquiterpenes in all the tissues. However, treatment with GA 3 seemed to block polyphenol synthesis, mainly in berries. In conclusion, ABA and GA

Machine‐Assisted Organic Synthesis

PubMed Central

Fitzpatrick, Daniel E.; Myers, Rebecca M.; Battilocchio, Claudio; Ingham, Richard. J.

2015-01-01

Abstract 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. PMID:26193360

The energetics of organic synthesis inside and outside the cell

PubMed Central

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

2013-01-01

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

Prebiotic organic synthesis under hydrothermal conditions: an overview

NASA Astrophysics Data System (ADS)

Simoneit, Bernd R. T.

Organic compounds which are obviously synthesized from inorganic precursors (e.g., CO) by hydrothermal activity are currently a research topic in prebiotic chemistry leading to the origin of life. However, such de novo products would be overwhelmed in present Earth environments, by an excess of thermal alteration (pyrolysis) products formed from contemporary life (e.g., hydrocarbons, alkanoic acids, etc.). Thus, organic syntheses must be demonstrated and distinguished from organic matter alteration initially in the laboratory and then in the field. Organic synthesis under hydrothermal conditions is theoretically possible and various established industrial processes are used to synthesize organic compounds from inorganic substrates with the aid of catalysts. A set of Strecker-type synthesis experiments has been carried out under hydrothermal conditions (150 °C), producing various amino acids. The formation of lipid compounds during an aqueous organic synthesis (Fischer-Tropsch-type) reaction was reported, using solutions of oxalic acid (also formic acid) as the carbon and hydrogen sources, and heating at discrete temperatures (50° intervals) from 100 to 400 °C. The maximum lipid yield, especially for oxygenated compounds was in the window of 150-250 °C. The compounds range from C6 to >C33, including n-alkanols, n-alkanoic acids, n-alkyl formates, n-alkanones, and n-alkanes, all with no carbon number preferences. These lipid compounds, especially the acids, can form lipid bilayers or micelles, potential precursors for membranes. Reductive condensation (i.e., dehydration) reactions also occur under simulated hydrothermal conditions and form amide, nitrile and ester bonds. The chemistry and kinetics of the condensation reactions are under further study and have the potential for oligomerization of acid-amides in aqueous medium. Abiotic organic compounds are not biomarkers per se because they do not originate from biosynthesis. Thus, they should be regarded as a

Prebiotic Organic Synthesis under Hydrothermal Conditions - An Overview

NASA Astrophysics Data System (ADS)

Simoneit, B.

Organic compounds which are obviously synthesized from inorganic precursors (e.g., CO) by hydrothermal activity are currently a research topic in prebiotic chemistry leading to the origin of life. However, such de novo products would be overwhelmed in present Earth environments, by an excess of thermal alteration (pyrolysis) products formed from contemporary life (e.g., hydrocarbons, alkanoic acids, etc.). Thus, organic syntheses must be demonstrated and distinguished from organic matter alteration initially in the laboratory and then in the field. Organic synthesis under hydrothermal conditions is theoretically possible and various established industrial processes are used to synthesize organic compounds from inorganic substrates with the aid of catalysts. A set of Strecker-type synthesis experiments has been carried out under hydrothermal conditions (150°C), producing various amino acids. The formation of lipid compounds during an aqueous organic synthesis (Fischer-Tropsch-type) reaction was reported, using solutions of oxalic acid (also formic acid) as the carbon and hydrogen sources, and heating at discrete temperatures (50° intervals) from 100- 400°C. The maximum lipid yield, especially for oxygenated compounds was in the window of 150-250°C. The compounds range from C6 to >C3 3 , including n-alkanols, n-alkanoic acids, n-alkyl formates, n-alkanones, and n-alkanes, all with no carbon number preferences. These lipid compounds, especially the acids, can form lipid bilayers or micelles, potential precursors for membranes. Reductive condensation (i.e., dehydration) reactions also occur under simulated hydrothermal conditions and form amide, nitrile and ester bonds. The chemistry and kinetics of the condensation reactions are under further study and have the potential for oligomerization of acid-amides in aqueous medium. Abiotic organic compounds are not biomarkers per se because they do not originate from biosynthesis. Thus, they should be regarded as a

Fluid Mechanics Optimising Organic Synthesis

NASA Astrophysics Data System (ADS)

Leivadarou, Evgenia; Dalziel, Stuart

2015-11-01

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

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

PubMed Central

Rizzi, Yanina S.; Monteoliva, Mariela I.; Fabro, Georgina; Grosso, Carola L.; Laróvere, Laura E.; Alvarez, María E.

2015-01-01

Plants facing adverse conditions usually alter proline (Pro) metabolism, generating changes that help restore the cellular homeostasis. These organisms synthesize Pro from glutamate (Glu) or ornithine (Orn) by two-step reactions that share Δ1 pyrroline-5-carboxylate (P5C) as intermediate. In the catabolic process, Pro is converted back to Glu using a different pathway that involves Pro dehydrogenase (ProDH), P5C dehydrogenase (P5CDH), and P5C as intermediate. Little is known about the coordination of the catabolic and biosynthetic routes under stress. To address this issue, we analyzed how P5CDH affects the activation of Pro synthesis, in Arabidopsis tissues that increase ProDH activity by transient exposure to exogenous Pro, or infection with Pseudomonas syringae pv. tomato. Wild-type (Col-0) and p5cdh mutant plants subjected to these treatments were used to monitor the Pro, Glu, and Orn levels, as well as the expression of genes from Pro metabolism. Col-0 and p5cdh tissues consecutively activated ProDH and Pro biosynthetic genes under both conditions. However, they manifested a different coordination between these routes. When external Pro supply was interrupted, wild-type leaves degraded Pro to basal levels at which point Pro synthesis, mainly via Glu, became activated. Under the same condition, p5cdh leaves sustained ProDH induction without reducing the Pro content but rather increasing it, apparently by stimulating the Orn pathway. In response to pathogen infection, both genotypes showed similar trends. While Col-0 plants seemed to induce both Pro biosynthetic routes, p5cdh mutant plants may primarily activate the Orn route. Our study contributes to the functional characterization of P5CDH in biotic and abiotic stress conditions, by revealing its capacity to modulate the fate of P5C, and prevalence of Orn or Glu as Pro precursors in tissues that initially consumed Pro. PMID:26284090

Molybdenum compounds in organic synthesis

NASA Astrophysics Data System (ADS)

Khusnutdinov, R. I.; Oshnyakova, T. M.; Dzhemilev, U. M.

2017-02-01

The review presents the first analysis and systematic discussion of data published in the last 35-40 years on the use of molybdenum compounds and complexes in organic synthesis and catalysis of various ion coordination and radical reactions. Detailed account is given of the key trends in the use of molybdenum complexes as catalysts of alkene epoxidation and oxyketonation, oxidation of sulfur, nitrogen and phosphorus compounds, hydrosilylation of 1,3-dienes, ketones and aldehydes, hydrostannylation of acetylenes and hydrogermylation of norbornadienes. Considerable attention is paid to the description of new reactions and in situ generation of highly reactive hypohalites, ROX and HOX, induced by molybdenum complexes and the use of hypohalites in oxidative transformations. Data on the application of molybdenum complexes in well-known reactions are discussed, including Kharasch and Pauson-Khand reactions, allylic alkylation of C-nucleophiles, aminocarbonylation of halo derivatives and oligomerization of cyclic dienes, trienes, alkynes and 1,3-dienes. The last Section of the review considers 'unusual' organic reactions involving molybdenum compounds and complexes. The bibliography includes 257 references.

Rice Phospholipase A Superfamily: Organization, Phylogenetic and Expression Analysis during Abiotic Stresses and Development

PubMed Central

Singh, Amarjeet; Baranwal, Vinay; Shankar, Alka; Kanwar, Poonam; Ranjan, Rajeev; Yadav, Sandeep; Pandey, Amita; Kapoor, Sanjay; Pandey, Girdhar K.

2012-01-01

Background Phospholipase A (PLA) is an important group of enzymes responsible for phospholipid hydrolysis in lipid signaling. PLAs have been implicated in abiotic stress signaling and developmental events in various plants species. Genome-wide analysis of PLA superfamily has been carried out in dicot plant Arabidopsis. A comprehensive genome-wide analysis of PLAs has not been presented yet in crop plant rice. Methodology/Principal Findings A comprehensive bioinformatics analysis identified a total of 31 PLA encoding genes in the rice genome, which are divided into three classes; phospholipase A1 (PLA1), patatin like phospholipases (pPLA) and low molecular weight secretory phospholipase A2 (sPLA2) based on their sequences and phylogeny. A subset of 10 rice PLAs exhibited chromosomal duplication, emphasizing the role of duplication in the expansion of this gene family in rice. Microarray expression profiling revealed a number of PLA members expressing differentially and significantly under abiotic stresses and reproductive development. Comparative expression analysis with Arabidopsis PLAs revealed a high degree of functional conservation between the orthologs in two plant species, which also indicated the vital role of PLAs in stress signaling and plant development across different plant species. Moreover, sub-cellular localization of a few candidates suggests their differential localization and functional role in the lipid signaling. Conclusion/Significance The comprehensive analysis and expression profiling would provide a critical platform for the functional characterization of the candidate PLA genes in crop plants. PMID:22363522

Minerals Masquerading As Enzymes: Abiotic Oxidation Of Soil Organic Matter In An Iron-Rich Humid Tropical Forest Soil

NASA Astrophysics Data System (ADS)

Hall, S. J.; Silver, W. L.

2010-12-01

Oxidative reactions play an important role in decomposing soil organic matter fractions that resist hydrolytic degradation, and fundamentally affect the cycling of recalcitrant soil carbon across ecosystems. Microbial extracellular oxidative enzymes (e.g. lignin peroxidases and laccases) have been assumed to provide a dominant role in catalyzing soil organic matter oxidation, while other potential oxidative mechanisms remain poorly explored. Here, we show that abiotic reactions mediated by the oxidation of ferrous iron (Fe(II)) could explain high potential oxidation rates in humid tropical forest soils, which often contain high concentrations of Fe(II) and experience rapid redox fluctuations between anaerobic and aerobic conditions. These abiotic reactions could provide an additional mechanism to explain high rates of decomposition in these ecosystems, despite frequent oxygen deficits. We sampled humid tropical forest soils in Puerto Rico, USA from various topographic positions, ranging from well-drained ridges to riparian valleys that experience broad fluctuations in redox potential. We measured oxidative activity by adding the model humic compound L-DOPA to soil slurries, followed by colorimetric measurements of the supernatant solution over time. Dilute hydrogen peroxide was added to a subset of slurries to measure peroxidative activity. We found that oxidative and peroxidative activity correlated positively with soil Fe(II) concentrations, counter to prevailing theory that low redox potential should suppress oxidative enzymes. Boiling or autoclaving sub-samples of soil slurries to denature any enzymes present typically increased peroxidative activity and did not eliminate oxidative activity, further suggesting the importance of an abiotic mechanism. We found substantial differences in the oxidation products of the L-DOPA substrate generated by our soil slurries in comparison with oxidation products generated by a purified enzyme (mushroom tyrosinase

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

PubMed

O'Brien, Jeffrey; Shea, Kenneth J

2016-06-21

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

Synthesis Road Map Problems in Organic Chemistry

ERIC Educational Resources Information Center

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

2014-01-01

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

Organic synthesis in a changing world.

PubMed

Ley, Steven V; Baxendale, Ian R

2002-01-01

This article is based on a lecture presented to the Chemical Society of Japan at Wasada University on March 27, 2002, by Professor Steven V. Ley. The lecture, "Organic Synthesis in a Changing World," was a comprehensive account of the ongoing research efforts of professor Ley's group in the development and application of solid-supported reagents and scavengers for use in organic synthesis. Copyright 2002 The Japan Chemical Journal Forum and Wiley Periodicals, Inc.

Carbonyl sulfide produced by abiotic thermal and photodegradation of soil organic matter from wheat field substrate

NASA Astrophysics Data System (ADS)

Whelan, Mary E.; Rhew, Robert C.

2015-01-01

Carbonyl sulfide (COS) is a reduced sulfur gas that is taken up irreversibly in plant leaves proportionally with CO2, allowing its potential use as a tracer for gross primary production. Recently, wheat field soil at the Southern Great Plains Atmospheric Radiation Measurement site in Lamont, Oklahoma, was found to be a measureable source of COS to the atmosphere. To understand the mechanism of COS production, soil and root samples were collected from the site and incubated in the laboratory over a range of temperatures (15-34°C) and light conditions (light and dark). Samples exhibited mostly COS net uptake from the atmosphere in dark and cool (<22-25°C) trials. COS emission was observed during dark incubations at high temperatures (>25°C), consistent with field observations, and at a lower temperature (19°C) when a full spectrum lamp (max wavelength 600 nm) was applied. Sterilized soil and root samples yielded only COS production that increased with temperature, supporting the hypothesis that (a) COS production in these samples is abiotic, (b) production is directly influenced by temperature and light, and (c) some COS consumption in soil and root samples is biotic.

Underground Organic-Rich Fluids on Mars: Biotic vs Abiotic Processes

NASA Astrophysics Data System (ADS)

Lin, Y.; El Goresy, A.; Hu, S.; Zhang, J.; Gillet, P.; Xu, Y.; Hao, J.; Miyahara, M.; Ouyang, Z.; Ohtani, E.; Xu, L.; Yang, W.; Feng, L.; Zhao, X.; Yang, J.; Ozawa, S.

2013-09-01

We report kerogen-like organic carbon in fractures of silicates and a few in shock melt veins in the Tissint Martian meteorite. The D-enrichment evidences for a Martian origin, and the δ^13C down to -33 permil is consistent with a biogenic origin.

Influence of Dissolved Organic Matter and Fe (II) on the Abiotic Reduction of Pentachloronitrobenzene

EPA Science Inventory

Nitroaromatic pesticides (NAPs) are hydrophobic contaminants that can accumulate in sediments by the deposition of suspended solids from surface waters. Fe(II) and dissolved organic matter (DOM), present in suboxic and anoxic zones of freshwater sediments, can transform NAPs in n...

ABIOTIC REDOX TRANSFORMATION OF ORGANIC COMPOUNDS AT THE CLAY-WATER INTERFACE

EPA Science Inventory

The interactions of clay, water and organic compounds considerably modify the structural and physico-chemical properties of all components and create a unique domain for biological and chemical species in environments. Previous research indicates that the nature and properties of...

Abiotic vs biological sources and fates of organic compounds in a low temperature continental serpentinizing system

NASA Astrophysics Data System (ADS)

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

2016-12-01

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

The composition of the primitive atmosphere and the synthesis of organic compounds on the early Earth

NASA Technical Reports Server (NTRS)

Bada, J. L.; Miller, S. L.

1985-01-01

The generally accepted theory for the origin of life on the Earth requires that a large variety of organic compounds be present to form the first living organisms and to provide the energy sources for primitive life either directly or through various fermentation reactions. This can provide a strong constraint on discussions of the formation of the Earth and on the composition of the primitive atmosphere. In order for substantial amounts of organic compounds to have been present on the prebiological Earth, certain conditions must have existed. There is a large body of literature on the prebiotic synthesis of organic compounds in various postulated atmospheres. In this mixture of abiotically synthesized organic compounds, the amino acids are of special interest since they are utilized by modern organisms to synthesize structural materials and a large array of catalytic peptides.

Magnetically retrievable catalysts for organic synthesis

EPA Science Inventory

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

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

NASA Technical Reports Server (NTRS)

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

2015-01-01

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

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

NASA Technical Reports Server (NTRS)

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

2011-01-01

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

Endogenous Synthesis of Prebiotic Organic Molecules

NASA Technical Reports Server (NTRS)

Miller, Stanley L.

1996-01-01

The necessary condition for the synthesis of organic compounds on the primitive earth is the presence of reducing conditions. This means an atmosphere of CH4, CO, or CO2 + H2. The atmospheric nitrogen can be N2 with a trace of NH3, but NH4(+) is needed in the ocean at least for amino acid synthesis. Many attempts have been made to use CO2 + H2O atmospheres for prebiotic synthesis, but these give at best extremely low yields of organic compounds, except in the presence of H2. Even strong reducing agents such as FeS + H2S or the mineral assemblages of the submarine vents fail to give significant yields of organic compounds with CO2. There appears to be a high kinetic barrier to the non-biological reduction of CO2 at low temperatures using geological reducing agents. The most abundant source of energy for prebiotic synthesis is ultraviolet light followed by electric discharges, with electric discharges being more efficient, although it is not clear which was the important energy source. Photochemical process would also make significant contributions. In an atmosphere Of CO2, N2, and H2O with no H2, the production rates of HCN and H2CO would be very low, 0.001 or less than that of a relatively reducing atmosphere. The concentration of organic compounds under these non-reducing conditions would be so low that there is doubt whether the concentration mechanism would be adequate for further steps toward the origin of life. A number of workers have calculated the influx of comets and meteorites on the primitive earth as a source of organic compounds. We conclude that while some organic material was added to the earth from comets and meteorites the amount available from these sources at a given time was at best only a few percent of that from earth bases syntheses under reducing conditions.

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

PubMed Central

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

2008-01-01

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

Richard Schrock, Robert Grubbs, and Metathesis Method in Organic Synthesis

Science.gov Websites

Organic Synthesis Resources with Additional Information Richard R. Schrock of the Massachusetts Institute Nobel Prize in Chemistry "for the development of the metathesis method in organic synthesis" ] Chauvin, Grubbs and Schrock "for the development of the metathesis method in organic synthesis,"

Abiotic Supramolecular Systems

DTIC Science & Technology

2011-05-02

REPORT Abiotic Supramolecular Systems 14. ABSTRACT 16. SECURITY CLASSIFICATION OF: The goal of this research project was to develop new concepts for the...decision, unless so designated by other documentation. 12. DISTRIBUTION AVAILIBILITY STATEMENT Approved for Public Release; Distribution Unlimited UU...9. SPONSORING/MONITORING AGENCY NAME(S) AND ADDRESS(ES) 6. AUTHORS 7. PERFORMING ORGANIZATION NAMES AND ADDRESSES U.S. Army Research Office P.O

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

NASA Technical Reports Server (NTRS)

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

2014-01-01

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

Organic synthesis in experimental impact shocks

NASA Technical Reports Server (NTRS)

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

1997-01-01

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

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

NASA Technical Reports Server (NTRS)

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

2014-01-01

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

Synthesis-Spectroscopy Roadmap Problems: Discovering Organic Chemistry

ERIC Educational Resources Information Center

Kurth, Laurie L.; Kurth, Mark J.

2014-01-01

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

Novel Aryne Chemistry in Organic Synthesis

SciTech Connect

Liu, Zhijian

2006-12-12

Arynes are among the most intensively studied systems in chemistry. However, many aspects of the chemistry of these reactive intermediates are not well understood yet and their use as reagents in synthetic organic chemistry has been somewhat limited, due to the harsh conditions needed to generate arynes and the often uncontrolled reactivity exhibited by these species. Recently, o-silylaryl triflates, which can generate the corresponding arynes under very mild reaction conditions, have been found very useful in organic synthesis. This thesis describes several novel and useful methodologies by employing arynes, which generate from o-silylaryl triflates, in organic synthesis. An efficient, reliablemore » 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

Lipoxygenase6-Dependent Oxylipin Synthesis in Roots Is Required for Abiotic and Biotic Stress Resistance of Arabidopsis1[C][W

PubMed Central

Grebner, Wiebke; Stingl, Nadja E.; Oenel, Ayla; Mueller, Martin J.; Berger, Susanne

2013-01-01

Jasmonates are oxylipin signals that play important roles in the development of fertile flowers and in defense against pathogens and herbivores in leaves. The aim of this work was to understand the synthesis and function of jasmonates in roots. Grafting experiments with a jasmonate-deficient mutant demonstrated that roots produce jasmonates independently of leaves, despite low expression of biosynthetic enzymes. Levels of 12-oxo-phytodienoic acid, jasmonic acid, and its isoleucine derivative increased in roots upon osmotic and drought stress. Wounding resulted in a decrease of preformed 12-oxo-phytodienoic acid concomitant with an increase of jasmonic acid and jasmonoyl-isoleucine. 13-Lipoxygenases catalyze the first step of lipid oxidation leading to jasmonate production. Analysis of 13-lipoxygenase-deficient mutant lines showed that only one of the four 13-lipoxygenases, LOX6, is responsible and essential for stress-induced jasmonate accumulation in roots. In addition, LOX6 was required for production of basal 12-oxo-phytodienoic acid in leaves and roots. Loss-of-function mutants of LOX6 were more attractive to a detritivorous crustacean and more sensitive to drought, indicating that LOX6-derived oxylipins are important for the responses to abiotic and biotic factors. PMID:23444343

The Combined Role Of Manganese Oxides And Microbes In The yAbiotic Uptake Of Amino Acid Nitrogen Into Litter And Soil Organic yMatter

NASA Astrophysics Data System (ADS)

Filley, T. R.; Dria, K.

2004-12-01

Soil organic matter (SOM) is the largest terrestrial C and N store. Microbial yand abiotic processes that control the transformation of protein nitrogen in litter and ysoils into macromolecular humic materials play an important role in organic matter ystorage and soil productivity. There are major gaps, however, in our understanding of ythese processes and behaviors. Abiotic reactions of amines, phenols and sugars derived yfrom forest leachates or present in detrital and litter organic matter are known to be ykey processes in the formation of complex organic nitrogen. We present here the yresults from a study designed to investigate how the inherent chemistry of lignin, leaf ylitter, and progressively advanced brown-rot wood decay impact the chemical reaction yof amino acids with this organic matter. Additionally, experiments in the presence of ybirnessite (MnO2) were also conducted to investigate the role of mineral induced phenol yoxidation on specific amino acid chemical humifcation processes. Solid and liquid state yNMR, 13C-labelled tetramethyl ammonium hydroxide thermochemolysis and stable ycarbon and nitrogen isotope ratio mass spectrometry were used to track the alteration yof litter material and document uptake of 13C and 15N labeled amino acids. yPreliminary results from birnessite-containing experiments suggest that the metal-ypromoted oxidation of the lignin, leaf litter, and, in particular, demethylated brown rot ywood residues, is necessary to convert the phenols to quinones of some type permitting yamine addition. This relationship is particularly true for the production of soluble yfractions after two and six weeks of reaction in the presence of the manganese oxides. yAdditionally, the production of leachable organic matter with incorporated N was ypromoted in the soluble fractions. Ongoing NMR studies will elucidate the nature of ythe chemical binding in these experiments. y

Organic synthesis: march of the machines.

PubMed

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

2015-03-09

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.

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

PubMed Central

2015-01-01

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

Interactive effects of MnO2, organic matter and pH on abiotic formation of N2O from hydroxylamine in artificial soil mixtures.

PubMed

Liu, Shurong; Berns, Anne E; Vereecken, Harry; Wu, Di; Brüggemann, Nicolas

2017-02-01

Abiotic conversion of the reactive nitrification intermediate hydroxylamine (NH 2 OH) to nitrous oxide (N 2 O) is a possible mechanism of N 2 O formation during nitrification. Previous research has demonstrated that manganese dioxide (MnO 2 ) and organic matter (OM) content of soil as well as soil pH are important control variables of N 2 O formation in the soil. But until now, their combined effect on abiotic N 2 O formation from NH 2 OH has not been quantified. Here, we present results from a full-factorial experiment with artificial soil mixtures at five different levels of pH, MnO 2 and OM, respectively, and quantified the interactive effects of the three variables on the NH 2 OH-to-N 2 O conversion ratio (R NH2OH-to-N2O ). Furthermore, the effect of OM quality on R NH2OH-to-N2O was determined by the addition of four different organic materials with different C/N ratios to the artificial soil mixtures. The experiments revealed a strong interactive effect of soil pH, MnO 2 and OM on R NH2OH-to-N2O . In general, increasing MnO 2 and decreasing pH increased R NH2OH-to-N2O , while increasing OM content was associated with a decrease in R NH2OH-to-N2O . Organic matter quality also affected R NH2OH-to-N2O . However, this effect was not a function of C/N ratio, but was rather related to differences in the dominating functional groups between the different organic materials.

Interactive effects of MnO2, organic matter and pH on abiotic formation of N2O from hydroxylamine in artificial soil mixtures

NASA Astrophysics Data System (ADS)

Liu, Shurong; Berns, Anne E.; Vereecken, Harry; Wu, Di; Brüggemann, Nicolas

2017-02-01

Abiotic conversion of the reactive nitrification intermediate hydroxylamine (NH2OH) to nitrous oxide (N2O) is a possible mechanism of N2O formation during nitrification. Previous research has demonstrated that manganese dioxide (MnO2) and organic matter (OM) content of soil as well as soil pH are important control variables of N2O formation in the soil. But until now, their combined effect on abiotic N2O formation from NH2OH has not been quantified. Here, we present results from a full-factorial experiment with artificial soil mixtures at five different levels of pH, MnO2 and OM, respectively, and quantified the interactive effects of the three variables on the NH2OH-to-N2O conversion ratio (RNH2OH-to-N2O). Furthermore, the effect of OM quality on RNH2OH-to-N2O was determined by the addition of four different organic materials with different C/N ratios to the artificial soil mixtures. The experiments revealed a strong interactive effect of soil pH, MnO2 and OM on RNH2OH-to-N2O. In general, increasing MnO2 and decreasing pH increased RNH2OH-to-N2O, while increasing OM content was associated with a decrease in RNH2OH-to-N2O. Organic matter quality also affected RNH2OH-to-N2O. However, this effect was not a function of C/N ratio, but was rather related to differences in the dominating functional groups between the different organic materials.

Organic or organometallic template mediated clay synthesis

DOEpatents

Gregar, Kathleen C.; Winans, Randall E.; Botto, Robert E.

1994-01-01

A method 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 lithium fluoride for two days in the presence of 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 that are 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 U.S. Pat. No. 3,887,454 issued to Hickson, Jun. 13, 1975; however, a variety of intercalants or templates may be introduced. The intercalants or templates should have (i) water-solubility, (ii) positive charge, and (iii) thermal stability under moderately basic (pH 9-10) aqueous reflux conditions or hydrothermal pressurized conditions for the montmorillonite-type clays.

Organic or organometallic template mediated clay synthesis

DOEpatents

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

1994-05-03

A method is described for incorporating diverse varieties of intercalates 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 lithium fluoride for two days in the presence of an organic or organometallic intercalate 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 that are 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 U.S. Pat. No. 3,887,454 issued to Hickson, Jun. 13, 1975; however, a variety of intercalates or templates may be introduced. The intercalates or templates should have (i) water-solubility, (ii) positive charge, and (iii) thermal stability under moderately basic (pH 9-10) aqueous reflux conditions or hydrothermal pressurized conditions for the montmorillonite-type clays. 22 figures.

How Do Students Work through Organic Synthesis Learning Activities?

ERIC Educational Resources Information Center

Flynn, Alison B.

2014-01-01

Organic chemistry has the long-standing reputation as a challenging course, and organic synthesis is an aspect of organic chemistry that requires students to make the most links between concepts and requires the highest order of thinking. One-on-one interviews were conducted with students from a second undergraduate organic chemistry course in…

Mechanochemical synthesis of organic compounds and composites with their participation

NASA Astrophysics Data System (ADS)

Lyakhov, Nikolai Z.; Grigorieva, Tatiana F.; Barinova, Antonina P.; Vorsina, I. A.

2010-05-01

The results of experimental studies in the mechanochemical synthesis of organic compounds and composites with their participation published over the last 15 years are described systematically. The key reactions of organic compounds are considered: synthesis of the salts of organic acids, acylation, substitution, dehalogenation, esterification, hydrometallation and other reactions. Primary attention is devoted to systems and compounds that cannot be obtained by traditional chemistry methods.

Synthesis of fluorinated organic compounds using oxygen difluoride

NASA Technical Reports Server (NTRS)

Toy, M. S.

1971-01-01

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

Greener and Sustainable Trends in Synthesis of Organics and Nanomaterials

EPA Science Inventory

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...

Microwave-assisted 'greener' synthesis of organics and nanomaterials

EPA Science Inventory

Microwave selective heating techniques in conjunction with greener reaction media are dramatically reducing chemical waste and reaction times in several organic transformations and material synthesis. This presentation summarizes author’s own experience in developing MW-assisted ...

Microwave-assisted synthesis of organics and nanomaterials

EPA Science Inventory

Microwave-assisted chemistry techniques and greener reaction media are dramatically reducing chemical waste and reaction times in several organic transformations and material synthesis. This presentation summarizes author’s own experience in developing MW-assisted chemical proces...

Synthesis of Organic Compounds (Selected Articles)

DTIC Science & Technology

1990-10-03

OH+TiCI,+4NH3 - (CH2+CHCH 2 0)4 Ti+4NH4 Cl Allyl ester of-orthotitanium acid is obtained for the first time [1]. The proposed method is based on the...reaction of allyl alcohol with titanium tetrachloride in the presence of ammonia in the medium of benzene. DESCRIPTION OF SYNTHESIS Synthesis is...point 141-1420 at I mm: it is hygroscopic and easily hydrolized. NOTE Synthesis can be carried out in the absence of benzene in the medium of allyl

Biocatalyzed Regioselective Synthesis in Undergraduate Organic Laboratories: Multistep Synthesis of 2-Arachidonoylglycerol

ERIC Educational Resources Information Center

Johnston, Meghan R.; Makriyannis, Alexandros; Whitten, Kyle M.; Drew, Olivia C.; Best, Fiona A.

2016-01-01

In order to introduce the concepts of biocatalysis and its utility in synthesis to organic chemistry students, a multistep synthesis of endogenous cannabinergic ligand 2-arachidonoylglycerol (2-AG) was tailored for use as a laboratory exercise. Over four weeks, students successfully produced 2-AG, purifying and characterizing products at each…

Recent developments on ultrasound assisted catalyst-free organic synthesis.

PubMed

Banerjee, Bubun

2017-03-01

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.

Camera-enabled techniques for organic synthesis

PubMed Central

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

2013-01-01

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

"Crown Ether" Synthesis: An Organic Laboratory Experiment.

ERIC Educational Resources Information Center

Field, Kurt W.; And Others

1979-01-01

This experiment is designed to acquaint the student with a macromolecular synthesis of a crown ether type compound. The starting materials are readily available and the product, a cyclic polyether, belongs to a class of compounds that has aroused the interest of chemist and biologist alike. (Author/BB)

A Multistep Synthesis for an Advanced Undergraduate Organic Chemistry Laboratory

ERIC Educational Resources Information Center

Chang Ji; Peters, Dennis G.

2006-01-01

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

Synthesis of Ibuprofen in the Introductory Organic Laboratory

ERIC Educational Resources Information Center

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

2011-01-01

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

Recent progress in the synthesis of metal–organic frameworks

DOE PAGES

Sun, Yujia; Zhou, Hong -Cai

2015-09-25

Metal–organic frameworks (MOFs) have attracted considerable attention for various applications due to their tunable structure, porosity and functionality. In general, MOFs have been synthesized from isolated metal ions and organic linkers under hydrothermal or solvothermal conditions via one-spot reactions. The emerging precursor approach and kinetically tuned dimensional augmentation strategy add more diversity to this field. In addition, to speed up the crystallization process and create uniform crystals with reduced size, many alternative synthesis routes have been explored. Recent advances in microwave-assisted synthesis and electrochemical synthesis are presented in this review. In recent years, post-synthetic approaches have been shown to bemore » powerful tools to synthesize MOFs with modified functionality, which cannot be attained via de novo synthesis. In this study, some current accomplishments of post-synthetic modification (PSM) based on covalent transformations and coordinative interactions as well as post-synthetic exchange (PSE) in robust MOFs are provided.« less

Multiphase organic synthesis in microchannel reactors.

PubMed

Kobayashi, Juta; Mori, Yuichiro; Kobayashi, Shū

2006-07-17

"Miniaturization" is one of the most important aspects in today's technology. Organic chemistry is no exception. The search for highly effective, controllable, environmentally friendly methods for preparing products is of prime importance. The development of multiphase organic reactions in microchannel reactors has gained significant importance in recent years to allow novel reactivity, and has led to many fruitful results that are not attainable in conventional reactors. This Focus Review aims to shed light on how effectively multiphase organic reactions can be conducted with microchannel reactors by providing examples of recent remarkable studies, which have been grouped on the basis of the phases involved.

Chromium metal organic frameworks and synthesis of metal organic frameworks

SciTech Connect

Zhou, Hong-Cai; Liu, Tian-Fu; Lian, Xizhen

The present invention relates to monocrystalline metal organic frameworks comprising chromium ions and carboxylate ligands and the use of the same, for example their use for storing a gas. The invention also relates to methods for preparing metal organic frameworks comprising chromium, titanium or iron ions and carboxylate ligands. The methods of the invention allow such metal organic frameworks to be prepared in monocrystalline or polycrystalline forms.

Creatine Synthesis: An Undergraduate Organic Chemistry Laboratory Experiment

ERIC Educational Resources Information Center

Smith, Andri L.; Tan, Paula

2006-01-01

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

Synthesis of Bisphenol Z: An Organic Chemistry Experiment

ERIC Educational Resources Information Center

Gregor, Richard W.

2012-01-01

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

Synthesis and Chemistry of Organic Geminal Di- and Triazides.

PubMed

Häring, Andreas P; Kirsch, Stefan F

2015-11-06

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

ULTRASOUND-ASSISTED ORGANIC SYNTHESIS: ALCOHOL OXIDATION AND OLEFIN EPOXIDATION

EPA Science Inventory

Ultrasound-assisted Organic Synthesis: Alcohol Oxidation and Olefin Epoxidation

Unnikrishnan R Pillai, Endalkachew Sahle-Demessie , Vasudevan Namboodiri, Quiming Zhao, Juluis Enriquez
U.S. EPA , 26 W. Martin Luther King Dr. , Cincinnati, OH 45268
Phone: 513-569-773...

Applications of microwave-accelerated organic synthesis

NASA Astrophysics Data System (ADS)

Majetich, George; Hicks, Rodgers

1995-04-01

A comparison of microwave vs conventional heating is presented for a variety of Diels-Alder reactions, ortho-Claisen rearrangements, ene reactions, alkyl bromide preparations, Finkelstein reactions, oxidations, esterifications, hydrolyses, Williamson ether syntheses and other common organic transformations. In general, microwave-promoted reactions proceed with significant decreases in reaction times and in comparable chemical yield.

Organic synthesis during fluid mixing in hydrothermal systems

NASA Astrophysics Data System (ADS)

Shock, Everett L.; Schulte, Mitchell D.

1998-12-01

Hydrothermal circulation can lead to fluid mixing on any planet with liquid water and a source of heat. Aqueous fluids with differing compositions, especially different oxidation states, are likely to be far from thermodynamic equilibrium when they mix, and provide a source of free energy that can drive organic synthesis from CO2 and H2, and/or supply a source of geochemical energy to chemolithoautotrophic organisms. Results are presented that quantify the potential for organic synthesis during unbuffered fluid mixing in present submarine hydrothermal systems, as well as hypothetical systems that may have existed on the early Earth and Mars. Dissolved hydrogen, present in submarine hydrothermal fluids owing to the high-temperature reduction of H2O as seawater reacts with oceanic crustal rocks, provides the reduction potential and the thermodynamic drive for organic synthesis from CO2 (or bicarbonate) as hydrothermal fluids mix with seawater. The potential for organic synthesis is a strong function of the H2 content of the hydrothermal fluid, which is, in turn, a function of the prevailing oxidation state controlled by the composition of the rock that hosts the hydrothermal system. Hydrothermal fluids with initial oxidation states at or below those set by the fayalite-magnetite-quartz mineral assemblage show the greatest potential for driving organic synthesis. These calculations show that it is thermodynamically possible for 100% of the carbon in the mixed fluid to be reduced to a mixture of carboxylic acids, alcohols, and ketones in the range 250-50°C as cold seawater mixes with the hydrothermal fluid. As the temperature drops, larger organic molecules are favored, which implies that fluid mixing could drive the geochemical equivalent of a metabolic system. This enormous reduction potential probably drives a large portion of the primary productivity around present seafloor hydrothermal vents and would have been present in hydrothermal systems on the early Earth

Abiotic tooth enamel

NASA Astrophysics Data System (ADS)

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

2017-03-01

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.

Organic Synthesis in Simulated Interstellar Ice Analogs

NASA Technical Reports Server (NTRS)

Dworkin, Jason P.; Bernstein, Max P.; Sandford, Scott A.; Allamandola, Louis J.; Deamer, David W.; Elsila, Jamie; Zare, Richard N.; DeVincenzi, Donald (Technical Monitor)

2001-01-01

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

Organic Synthesis in Simulated Interstellar Ice Analogs

NASA Technical Reports Server (NTRS)

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

2001-01-01

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

Ohmic Heating: An Emerging Concept in Organic Synthesis.

PubMed

Silva, Vera L M; Santos, Luis M N B F; Silva, Artur M S

2017-06-12

The ohmic heating also known as direct Joule heating, is an advanced thermal processing method, mainly used in the food industry to rapidly increase the temperature for either cooking or sterilization purposes. Its use in organic synthesis, in the heating of chemical reactors, is an emerging method that shows great potential, the development of which has started recently. This Concept article focuses on the use of ohmic heating as a new tool for organic synthesis. It presents the fundamentals of ohmic heating and makes a qualitative and quantitative comparison with other common heating methods. A brief description of the ohmic reactor prototype in operation is presented as well as recent examples of its use in organic synthesis at laboratory scale, thus showing the current state of the research. The advantages and limitations of this heating method, as well as its main current applications are also discussed. Finally, the prospects and potential implications of ohmic heating in future research in chemical synthesis are proposed. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

Code of Federal Regulations, 2010 CFR

2010-01-01

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

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

Code of Federal Regulations, 2012 CFR

2012-01-01

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

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

Code of Federal Regulations, 2013 CFR

2013-01-01

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

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

Code of Federal Regulations, 2011 CFR

2011-01-01

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

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

Code of Federal Regulations, 2014 CFR

2014-01-01

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

Computer-assisted design of organic synthesis

NASA Technical Reports Server (NTRS)

Kaminaka, H.

1986-01-01

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

Mechanochemical synthesis of small organic molecules

PubMed Central

Achar, Tapas Kumar; Bose, Anima

2017-01-01

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. PMID:29062410

Organic synthesis provides opportunities to transform drug discovery

NASA Astrophysics Data System (ADS)

Blakemore, David C.; Castro, Luis; Churcher, Ian; Rees, David C.; Thomas, Andrew W.; Wilson, David M.; Wood, Anthony

2018-04-01

Despite decades of ground-breaking research in academia, organic synthesis is still a rate-limiting factor in drug-discovery projects. Here we present some current challenges in synthetic organic chemistry from the perspective of the pharmaceutical industry and highlight problematic steps that, if overcome, would find extensive application in the discovery of transformational medicines. Significant synthesis challenges arise from the fact that drug molecules typically contain amines and N-heterocycles, as well as unprotected polar groups. There is also a need for new reactions that enable non-traditional disconnections, more C-H bond activation and late-stage functionalization, as well as stereoselectively substituted aliphatic heterocyclic ring synthesis, C-X or C-C bond formation. We also emphasize that syntheses compatible with biomacromolecules will find increasing use, while new technologies such as machine-assisted approaches and artificial intelligence for synthesis planning have the potential to dramatically accelerate the drug-discovery process. We believe that increasing collaboration between academic and industrial chemists is crucial to address the challenges outlined here.

Diagnosing Abiotic Degradation

EPA Science Inventory

The abiotic degradation of chlorinated solvents in ground water can be difficult to diagnose. Under current practice, most of the “evidence” is negative; specifically the apparent disappearance of chlorinated solvents with an accumulation of vinyl chloride, ethane, ethylene, or ...

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

NASA Astrophysics Data System (ADS)

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

2012-12-01

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

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

NASA Technical Reports Server (NTRS)

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

2014-01-01

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

Engineering and Applications of fungal laccases for organic synthesis

PubMed Central

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

2008-01-01

Laccases are multi-copper containing oxidases (EC 1.10.3.2), widely distributed in fungi, higher plants and bacteria. Laccase catalyses the oxidation of phenols, polyphenols and anilines by one-electron abstraction, with the concomitant reduction of oxygen to water in a four-electron transfer process. In the presence of small redox mediators, laccase offers a broader repertory of oxidations including non-phenolic substrates. Hence, fungal laccases are considered as ideal green catalysts of great biotechnological impact due to their few requirements (they only require air, and they produce water as the only by-product) and their broad substrate specificity, including direct bioelectrocatalysis. Thus, laccases and/or laccase-mediator systems find potential applications in bioremediation, paper pulp bleaching, finishing of textiles, bio-fuel cells and more. Significantly, laccases can be used in organic synthesis, as they can perform exquisite transformations ranging from the oxidation of functional groups to the heteromolecular coupling for production of new antibiotics derivatives, or the catalysis of key steps in the synthesis of complex natural products. In this review, the application of fungal laccases and their engineering by rational design and directed evolution for organic synthesis purposes are discussed. PMID:19019256

α-Imino Esters in Organic Synthesis: Recent Advances.

PubMed

Eftekhari-Sis, Bagher; Zirak, Maryam

2017-06-28

α-Imino esters are useful precursors for the synthesis of a variety of types of natural and unnatural α-amino acid derivatives, with a wide range of biological activities. Due to the adjacent ester group, α-imino esters are more reactive relative to other types of imines and undergo different kinds of reactions, including organometallics addition, metal catalyzed vinylation and alkynylation, aza-Henry, aza-Morita-Baylis-Hillman, imino-ene, Mannich-type, and cycloaddition reactions, as well as hydrogenation and reduction. This review discusses the mechanism, scope, and applications of the reactions of α-imino esters and related compounds in organic synthesis, covering the literature from the last 12 years.

Production of hydroxyl radicals from abiotic oxidation of pyrite by oxygen under circumneutral conditions in the presence of low-molecular-weight organic acids

NASA Astrophysics Data System (ADS)

Zhang, Peng; Yuan, Songhu

2017-12-01

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

Synthesis of Chemiluminescent Esters: A Combinatorial Synthesis Experiment for Organic Chemistry Students

ERIC Educational Resources Information Center

Duarte, Robert; Nielson, Janne T.; Dragojlovic, Veljko

2004-01-01

A group of techniques aimed at synthesizing a large number of structurally diverse compounds is called combinatorial synthesis. Synthesis of chemiluminescence esters using parallel combinatorial synthesis and mix-and-split combinatorial synthesis is experimented.

The Stable Isotope Fractionation of Abiotic Reactions: A Benchmark in the Detection of Life

NASA Technical Reports Server (NTRS)

Summers, David P.

2003-01-01

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

Synthesis and Characterization of Functionalized Metal-organic Frameworks

PubMed Central

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

2014-01-01

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

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

PubMed

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

2015-01-28

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

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.

PubMed

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

2017-07-01

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.

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

NASA Technical Reports Server (NTRS)

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

2010-01-01

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

Electrical energy sources for organic synthesis on the early earth

NASA Technical Reports Server (NTRS)

Chyba, Christopher; Sagan, Carl

1991-01-01

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

Synthesis of Ge-nanoparticles in organic solution

NASA Astrophysics Data System (ADS)

Pugsley, Andrew James

Much interest is focused on the synthesis of semiconductor particles from organic solution, in order to provide luminescent tracers for biological assays. However, group IV semiconductors have been largely neglected be cause of the lack of suitable nanoparticle formation reactions by solution-phase chemistries. A potentially useful new route to solution-based synthesis of nanocrystalline-Si,Ge involves the reaction between Zintl phases (NaSi, Mg 2Ge) that formally contain anionic semiconducting group species (Si-, Ge4-) and liquid phase SiCU, GeCU, etc. Luminescent nanoparticles formed by these reactions in organic solvents (e.g. diglyme) have been decribed in work from the Kauzlarich group at UC Davis (California, USA). The aim of this project has been to characterise the structural chemistry and luminescent properties of the products of the reaction, as well as following the course of the reaction in situ via synchrotron measurements. The product of the reaction has been characterised by TEM and x-ray absorption spectroscopy as well as other techniques. In order to analyse the x-ray absorption spectroscopy data, a number of model compounds have been studied, including the precursor material which was previously uncharacterised by this technique. An in situ reaction cell has been designed and built and used at a number of synchrotron beamlines to follow the course of the reaction. It has been found that the presence of even low concentrations of water can greatly affect the formation reaction, this is described herein.

Greener and Sustainable Trends in Synthesis of Organics and ...

EPA Pesticide Factsheets

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.

Synthesis of phthalocyanine derivatives as materials for organic photovoltaic cells

NASA Astrophysics Data System (ADS)

Collazo-Ramos, Aura

Organic photovoltaics (OPVs) are used to convert sunlight into electricity by using thin films of organic semiconductors. OPVs have the potential to produce low cost, lightweight, flexible devices with an eased manufacturing process. This technology contains the potential to increase the use of clean, sustainable solar energy, helping manage the global energy and environmental crisis that results majorly from the constant use of fossil fuels as an energy source. The ability to modulate the physical properties of organic molecules by tuning their chemical structure is an advantage for OPVs. Phthalocyanines (Pcs) are highly pi-conjugated synthetic porphyrin analogs that have been explored as active layer components in OPVs due to their high extinction coefficients and hole mobilities. The Pc structure can be modified by the introduction of metals in the core and the incorporation of substituents into the periphery. These modifications tend to tune the solubility, photophysical properties and condensed phase organization of Pcs. The research work in this dissertation describes improved methods towards substituted Pc derivatives addressing: (1) the use of mass spectrometry techniques for Pcs characterization, (2) efforts to achieve materials with near-infrared (NIR) absorption, and (3) the potential of Pc as electron-acceptor materials. Herein, the synthesis of a series of asymmetric and symmetric metallated Pcs has been established, which resulted in interesting chemical, photophysical and electrochemical properties. The materials investigated in this thesis increase the potential of Pcs as organic semiconductors for OPVs.

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

NASA Astrophysics Data System (ADS)

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

2018-01-01

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

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

ERIC Educational Resources Information Center

Demare, Patricia; Regla, Ignacio

2012-01-01

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

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

ERIC Educational Resources Information Center

Touaibia, Mohamed; Guay, Michel

2011-01-01

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

Root Systems of Individual Plants, and the Biotic and Abiotic Factors Controlling Their Depth and Distribution: a Synthesis Using a Global Database.

NASA Astrophysics Data System (ADS)

Tumber-Davila, S. J.; Schenk, H. J.; Jackson, R. B.

2017-12-01

This synthesis examines plant rooting distributions globally, by doubling the number of entries in the Root Systems of Individual Plants database (RSIP) created by Schenk and Jackson. Root systems influence many processes, including water and nutrient uptake and soil carbon storage. Root systems also mediate vegetation responses to changing climatic and environmental conditions. Therefore, a collective understanding of the importance of rooting systems to carbon sequestration, soil characteristics, hydrology, and climate, is needed. Current global models are limited by a poor understanding of the mechanisms affecting rooting, carbon stocks, and belowground biomass. This improved database contains an extensive bank of records describing the rooting system of individual plants, as well as detailed information on the climate and environment from which the observations are made. The expanded RSIP database will: 1) increase our understanding of rooting depths, lateral root spreads and above and belowground allometry; 2) improve the representation of plant rooting systems in Earth System Models; 3) enable studies of how climate change will alter and interact with plant species and functional groups in the future. We further focus on how plant rooting behavior responds to variations in climate and the environment, and create a model that can predict rooting behavior given a set of environmental conditions. Preliminary results suggest that high potential evapotranspiration and seasonality of precipitation are indicative of deeper rooting after accounting for plant growth form. When mapping predicted deep rooting by climate, we predict deepest rooting to occur in equatorial South America, Africa, and central India.

Synthesis of nanometer-sized sodalite without adding organic additives.

PubMed

Fan, Wei; Morozumi, Kazumasa; Kimura, Riichiro; Yokoi, Toshiyuki; Okubo, Tatsuya

2008-06-01

Aggregates (80 nm) of sodalite nanocrystals with crystallite sizes ranging from 20 to 40 nm have been synthesized from a sodium aluminosilicate solution at low temperature, without adding any organic additives, while paying attention to the key factors for the synthesis of nanosized zeolite crystals. The physical properties of nanosized sodalite crystals were characterized by X-ray diffraction, scanning electron microscopy, high-resolution transmission electron microscopy, 29Si solid-state magic-angle spinning (MAS) NMR, and N2 adsorption. As expected, the external surface area of nanosized sodalite crystals is significantly increased compared with that of microsized sodalite crystals. The size of synthesized sodalite crystals can be controlled from 20 nm to 10 microm. It is found that the preparation of a homogeneous aluminosilicate solution followed by the formation of an aluminosilicate hard gel by adjusting the initial composition, for example, SiO2/Al2O3 and Na2O/H2O ratios, is critical for synthesis.

[Evidence of benzo-3, 4-pyrene in the water and organic sediments of briny pools of polynesian atolls. Biotic and abiotic factors].

PubMed

Niaussat, P M; Trichet, J; Heros, M; Luong, N T; Ehrhardt, J P

1975-10-06

The presence of 3,4-benzopyrene is reported in samples of water and sediments from three briny ponds free from pollution of exogenous origin belonging to three different atolls of Polynesia. The synthesis of this hydrocarbon seems to be dependent on the presence of abundant phytoplancton and of bacterial flora.

Sustainable Strategies for the Synthesis of Organics and Nanomaterials

EPA Science Inventory

The presentation summarizes recent activity in eco-friendly chemical synthesis, which involves benign alternatives, such as the use of supported reagents, and greener reaction medium in aqueous or solvent-free conditions. The synthesis of heterocyclic compounds, coupling reaction...

Sustainable Alternatives for the Synthesis of Organics and Nanomaterials

EPA Science Inventory

The presentation summarizes recent activity in eco-friendly chemical synthesis, which involves benign alternatives, such as the use of supported reagents, and greener reaction medium in aqueous or solvent-free conditions. The synthesis of heterocyclic compounds, coupling reaction...

Organic synthesis toward small-molecule probes and drugs

PubMed Central

Schreiber, Stuart L.

2011-01-01

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

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

ERIC Educational Resources Information Center

Sichula, Vincent A.

2015-01-01

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

Abiotic methane formation during experimental serpentinization of olivine

PubMed Central

2016-01-01

Fluids circulating through actively serpentinizing systems are often highly enriched in methane (CH4). In many cases, the CH4 in these fluids is thought to derive from abiotic reduction of inorganic carbon, but the conditions under which this process can occur in natural systems remain unclear. In recent years, several studies have reported abiotic formation of CH4 during experimental serpentinization of olivine at temperatures at or below 200 °C. However, these results seem to contradict studies conducted at higher temperatures (300 °C to 400 °C), where substantial kinetic barriers to CH4 synthesis have been observed. Here, the potential for abiotic formation of CH4 from dissolved inorganic carbon during olivine serpentinization is reevaluated in a series of laboratory experiments conducted at 200 °C to 320 °C. A 13C-labeled inorganic carbon source was used to unambiguously determine the origin of CH4 generated in the experiments. Consistent with previous high-temperature studies, the results indicate that abiotic formation of CH4 from reduction of dissolved inorganic carbon during the experiments is extremely limited, with nearly all of the observed CH4 derived from background sources. The results indicate that the potential for abiotic synthesis of CH4 in low-temperature serpentinizing environments may be much more limited than some recent studies have suggested. However, more extensive production of CH4 was observed in one experiment performed under conditions that allowed an H2-rich vapor phase to form, suggesting that shallow serpentinization environments where a separate gas phase is present may be more favorable for abiotic synthesis of CH4. PMID:27821742

Abiotic methane formation during experimental serpentinization of olivine.

PubMed

McCollom, Thomas M

2016-12-06

Fluids circulating through actively serpentinizing systems are often highly enriched in methane (CH 4 ). In many cases, the CH 4 in these fluids is thought to derive from abiotic reduction of inorganic carbon, but the conditions under which this process can occur in natural systems remain unclear. In recent years, several studies have reported abiotic formation of CH 4 during experimental serpentinization of olivine at temperatures at or below 200 °C. However, these results seem to contradict studies conducted at higher temperatures (300 °C to 400 °C), where substantial kinetic barriers to CH 4 synthesis have been observed. Here, the potential for abiotic formation of CH 4 from dissolved inorganic carbon during olivine serpentinization is reevaluated in a series of laboratory experiments conducted at 200 °C to 320 °C. A 13 C-labeled inorganic carbon source was used to unambiguously determine the origin of CH 4 generated in the experiments. Consistent with previous high-temperature studies, the results indicate that abiotic formation of CH 4 from reduction of dissolved inorganic carbon during the experiments is extremely limited, with nearly all of the observed CH 4 derived from background sources. The results indicate that the potential for abiotic synthesis of CH 4 in low-temperature serpentinizing environments may be much more limited than some recent studies have suggested. However, more extensive production of CH 4 was observed in one experiment performed under conditions that allowed an H 2 -rich vapor phase to form, suggesting that shallow serpentinization environments where a separate gas phase is present may be more favorable for abiotic synthesis of CH 4 .

Nanostructured organic electronic materials: Synthesis and sensor applications

NASA Astrophysics Data System (ADS)

Dua, Vineet

2009-12-01

This study is an investigation into (a) the process by which one obtains bulk quantities of nanofibers of parent polythiophene, (b) in-situ deposition of nanofibers of polythiophene on flexible substrate and its application in vapor sensing, and (c) inkjet printing of graphene on flexible substrate and its application as a detector. (a) The 2 nd chapter of the thesis is an extension of "seeding" method from aqueous to organic solvents to synthesize parent polythiophene nanofibers. Bulk quantities of parent polythiophene nanofibers were synthesized in one step using catalytic amounts of freeze dried V2O5. This work is published in Chemistry Letters 2008 37(5), 526--527. (b) The 3rd chapter deals with in-situ films of polythiophene nanofibers on plastic substrates. In this a one step method to directly deposit nanofibers of parent polythiophene on flexible substrate is discussed. These films show a reversible detection of highly oxidizing vapors such as NO2, Cl2 and SO 2 at ppb levels under ambient conditions. This work is published in Macromolecules 2009, 42, 5414--5415. (c) The 4 th chapter describes the synthesis of reduced graphene oxide (RGO) using a mild reducing agent ascorbic acid (Vitamin C) rather than traditionally used harsh reducing agents (N2H4). Dispersions of RGO were inkjet printed on flexible substrate and has been shown to detect aggressive vapors NO2 and Cl2 at ambient conditions. This work is accepted for publication in Angewandte Chemie (Nov 2009).

Designing cooperatively folded abiotic uni- and multimolecular helix bundles

NASA Astrophysics Data System (ADS)

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

2018-01-01

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.

Strategies for the Green Synthesis of Organics and Nanomaterials

EPA Science Inventory

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 varie...

Sustainable Synthesis of Organics and Nanomaterials Using Microwave Irradiation

EPA Science Inventory

MW-assisted synthesis of heterocyclic compounds and nanomaterials under benign conditions is summarized. Shape-controlled aqueous synthesis of noble nanostructures via MW spontaneous reduction of metal salts using -D-glucose, sucrose, and maltose will be presented. A general met...

Abiotic gene transfer: rare or rampant?

PubMed Central

Kotnik, Tadej; Weaver, James C.

2016-01-01

Phylogenetic studies reveal that horizontal gene transfer (HGT) plays a prominent role in evolution and genetic variability of life. Five biotic mechanisms of HGT among prokaryotic organisms have been extensively characterized: conjugation, competence, transduction, gene-transfer-agent (GTA) particles, and transitory fusion with recombination, but it is not known whether they can account for all natural HGT. It is even less clear how HGT could have occurred before any of these mechanisms had developed. Here, we consider contemporary conditions and experiments on microorganisms to estimate possible roles of abiotic HGT – currently and throughout evolution. Candidate mechanisms include freeze-and-thaw, microbeads-agitation, and electroporation-based transformation, and we posit that these laboratory techniques have analogues in nature acting as mechanisms of abiotic HGT: freeze-and-thaw cycles in polar waters, sand-agitation at foreshores and riverbeds, and lightning-triggered electroporation in near-surface aqueous habitats. We derive conservative order-of-magnitude estimates for rates of microorganisms subjected to freeze-and-thaw cycles, sand-agitation, and lightning-triggered electroporation, at 1024, 1019, and 1017 per year, respectively. Considering the yield of viable transformants, which is by far the highest in electroporation, we argue this may still favor lightning-triggered transformation over the other two mechanisms. Electroporation-based gene transfer also appears to be the most general of these abiotic candidates, and perhaps even of all known HGT mechanisms. Future studies should provide improved estimates of gene transfer rates and cell viability, currently and in the past, but to assess the importance of abiotic HGT in nature, will likely require substantial progress – also in knowledge of biotic HGT. PMID:27067073

The Synthesis of a Cockroach Pheromone: An Experiment for the Second-Year Organic Chemistry Laboratory

ERIC Educational Resources Information Center

Feist, Patty L.

2008-01-01

This experiment describes the synthesis of gentisyl quinone isovalerate, or blattellaquinone, a sex pheromone of the German cockroach that was isolated and identified in 2005. The synthesis is appropriate for the second semester of a second-year organic chemistry laboratory course. It can be completed in two, three-hour laboratory periods and uses…

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

PubMed

Nicolaou, K C; Baran, Phil S

2002-08-02

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

Microwave-Assisted Chemistry: A Rapid and Sustainable Route to Synthesis of Organics and Nanomaterials

EPA Science Inventory

The use of emerging MW-assisted chemistry techniques in conjunction with benign reaction media is dramatically reducing chemical waste and reaction times in several organic syntheses and chemical transformations. This review summarizes recent developments in MW-assisted synthesis...

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

NASA Technical Reports Server (NTRS)

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

2010-01-01

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

Design and synthesis of inorganic/organic hybrid electrochemical materials

NASA Astrophysics Data System (ADS)

Harreld, John H.

An ambient pressure method for drying sol-gel materials is developed to synthesize high porosity (80--90%), high surface area vanadium oxide and silica aerogel materials (150--300 and 1000 m2/g for vanadium pentoxide and silica, respectively). The synthesis approach uses liquid exchange to replace the pore fluid with a low surface tension, nonpolar solvent which reduces the capillary pressures developed during drying. The Good-Girifalco interaction parameter is used to calculate pore stresses resulting from drying silica gels from various liquids. Vanadium oxide/polypyrrole hybrid aerogels are prepared using three strategies. These approaches focus on either sequential or consecutive polymerization of the inorganic and organic networks. Microcomposite aerogels are synthesized by encapsulating a dispersion of preformed polypyrrole in a vanadium pentoxide gel. In the second approach, pyrrole is polymerized and doped within the pore volume of preformed vanadium pentoxide gel. When the inorganic and organic precursors are polymerized simultaneously, the resulting gels exhibited a nanometer scaled microstructure with homogeneous distributions of either phases. Through this route, a suitable microstructure and composition for a lithium secondary battery cathode is obtained. Lithiated aerogels of hydrated nickel, cobalt, and mixed nickel-cobalt oxides are synthesized from lithium hydroxide and transition metal acetate precursors. The XRD analyses indicate that the nickel containing gels exhibit a lithium deficiency (less than 1 Li/transition metal. By increasing the concentration of the lithium precursor the lithium content in nickel oxides is increased, and additional base solution is no longer required to catalyze gelation. A non-hydrolytic sol-gel approach is utilized to create tin oxide and tin-aluminum binary oxide aerogels with high porosity (90%) and high surface area (300 m2/g). XRD data from single phase tin oxide aerogel indicates the growth of SnO2 crystallites

Abiotic and Biotic Formation of Amino Acids in the Enceladus Ocean.

PubMed

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

2017-09-01

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

Recent Developments in the Use of Organoboranes in Organic Synthesis

ERIC Educational Resources Information Center

Cragg, G. M. L.

1969-01-01

Describes how the carbonylation of organoboranes in a suitable solvent can produce various alcohols, ketones, aldehydes and oxymethylation derivatives. The synthesis of alpha-alkylated ketone using alkylboranes is discussed. (RR)

Abiotic stress signaling and responses in plants

PubMed Central

Zhu, Jian-Kang

2016-01-01

Summary As sessile organisms, plants must cope with abiotic stress such as soil salinity, drought, and extreme temperatures. Core stress signaling pathways involve protein kinases related to the yeast SNF1 and mammalian AMPK, suggesting that stress signaling in plants evolved from energy sensing. Stress signaling regulates proteins critical for ion and water transport and for metabolic and gene-expression reprogramming to bring about ionic and water homeostasis and cellular stability under stress conditions. Understanding stress signaling and responses will increase our ability to improve stress resistance in crops to achieve agricultural sustainability and food security for a growing world population. PMID:27716505

Eco-friendly Synthesis of Organics and Nanomaterials ...

EPA Pesticide Factsheets

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

Glycol-modified silanes: novel possibilities for the synthesis of hierarchically organized (hybrid) porous materials.

PubMed

Hartmann, Sarah; Brandhuber, Doris; Hüsing, Nicola

2007-09-01

The preparation of porous hierarchical architectures that have structural features spanning from the nanometer to micrometer and even larger dimensions and that exhibit certain functionalities is one of the new challenging frontiers in materials chemistry. The sol-gel process is one of the most promising synthesis routes toward such materials because it not only offers the possibility to incorporate organic functions into the porous host but also offers the possibility to deliberately tailor the pore structure. In this Account, the opportunities given by the application of novel diol-modified silanes are discussed for the synthesis of hierarchically organized inorganic and also inorganic-organic porous monoliths.

Plasmachemical synthesis of nanopowders of yttria and zirconia from dispersed water-salt-organic mixtures

NASA Astrophysics Data System (ADS)

Novoselov, Ivan; Karengin, Alexander; Shamanin, Igor; Alyukov, Evgeny; Gusev, Alexander

2018-03-01

Article represents results on theoretical and experimental research of yttria and zirconia plasmachemical synthesis in air plasma from water-salt-organic mixtures "yttrium nitrate-water-acetone" and "zirconyl nitrate-water-acetone". On the basis of thermotechnical calculations the influence of organic component on lower heat value and adiabatic combustion temperature of water-salt-organic mixtures as well as compositions of mixtures providing their energy-efficient plasma treatment were determined. The calculations found the influence of mass fraction and temperature of air plasma supporting gas on the composition of plasma treatment products. It was determined the conditions providing yttria and zirconia plasmachemical synthesis in air plasma. During experiments it was b eing carried out the plasmachemical synthesis of yttria and zirconia powders in air plasma flow from water -salt-organic mixtures. Analysis of the results for obtained powders (scanning electron microscopy, X-ray diffraction analysis, BET analysis) confirm nanostructure of yttria and zirconia.

Vinylphosphonium and 2-aminovinylphosphonium salts – preparation and applications in organic synthesis

PubMed Central

Mazurkiewicz, Roman; Fryczkowska, Beata

2017-01-01

The main synthetic routes towards vinylphosphonium salts and their wide applications in organic synthesis are discussed in this review. Particular attention is paid to the use of these compounds as building blocks for the synthesis of carbo- and heterocyclic systems after their prior transformation into the corresponding phosphorus ylides, followed by the intramolecular Wittig reaction with various types of nucleophiles containing a carbonyl function in their structures. PMID:29564008

Synthesis of the Commercial Fragrance Compound Ethyl 6-Acetoxyhexanoate: A Multistep Ester Experiment for the Second-Year Organic Laboratory

ERIC Educational Resources Information Center

McCullagh, James V.; Hirakis, Sophia P.

2017-01-01

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…

Widespread abiotic methane in chromitites.

PubMed

Etiope, G; Ifandi, E; Nazzari, M; Procesi, M; Tsikouras, B; Ventura, G; Steele, A; Tardini, R; Szatmari, P

2018-06-07

Recurring discoveries of abiotic methane in gas seeps and springs in ophiolites and peridotite massifs worldwide raised the question of where, in which rocks, methane was generated. Answers will impact the theories on life origin related to serpentinization of ultramafic rocks, and the origin of methane on rocky planets. Here we document, through molecular and isotopic analyses of gas liberated by rock crushing, that among the several mafic and ultramafic rocks composing classic ophiolites in Greece, i.e., serpentinite, peridotite, chromitite, gabbro, rodingite and basalt, only chromitites, characterized by high concentrations of chromium and ruthenium, host considerable amounts of 13 C-enriched methane, hydrogen and heavier hydrocarbons with inverse isotopic trend, which is typical of abiotic gas origin. Raman analyses are consistent with methane being occluded in widespread microfractures and porous serpentine- or chlorite-filled veins. Chromium and ruthenium may be key metal catalysts for methane production via Sabatier reaction. Chromitites may represent source rocks of abiotic methane on Earth and, potentially, on Mars.

Synthesis of soil geochemical characteristics and organic carbon degradation in Arctic polygon tundra, Barrow, Alaska

SciTech Connect

Zheng, Jianqiu; RoyChowdhury, Taniya; Herndon, Elizabeth

This is a synthesis data product that reports (1) the results of soil geochemical characterization and (2) organic carbon degradation in low temperature soil incubations on cores collected on the NGEE Arctic Study Area near Utqiaġvik (Barrow), Alaska. The study area consists of thaw lakes, drained thaw lake basins and interstitial tundra with a polygonal landscape of microtopographic features created by ice wedges. Integrated geochemical and organic carbon degradation data from 9 individual soil cores are included in the synthesis product.

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

NASA Technical Reports Server (NTRS)

Chang, S.

1982-01-01

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

Synthesis of Triptorelin Lactate Catalyzed by Lipase in Organic Media

PubMed Central

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

2012-01-01

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

Synthesis of triptorelin lactate catalyzed by lipase in organic media.

PubMed

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

2012-01-01

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

A new metalation complex for organic synthesis and polymerization reactions

NASA Technical Reports Server (NTRS)

Hirshfield, S. M.

1971-01-01

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

Hormone balance and abiotic stress tolerance in crop plants.

PubMed

Peleg, Zvi; Blumwald, Eduardo

2011-06-01

Plant hormones play central roles in the ability of plants to adapt to changing environments, by mediating growth, development, nutrient allocation, and source/sink transitions. Although ABA is the most studied stress-responsive hormone, the role of cytokinins, brassinosteroids, and auxins during environmental stress is emerging. Recent evidence indicated that plant hormones are involved in multiple processes. Cross-talk between the different plant hormones results in synergetic or antagonic interactions that play crucial roles in response of plants to abiotic stress. The characterization of the molecular mechanisms regulating hormone synthesis, signaling, and action are facilitating the modification of hormone biosynthetic pathways for the generation of transgenic crop plants with enhanced abiotic stress tolerance. Copyright © 2011 Elsevier Ltd. All rights reserved.

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

PubMed

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

2015-06-09

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.

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

PubMed Central

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

2015-01-01

In the nascent solar system, primitive organic matter was a major contributor of volatile elements to planetary bodies, and could have played a key role in the development of the biosphere. However, the origin of primitive organics is poorly understood. Most scenarios advocate cold synthesis in the interstellar medium or in the outer solar system. Here, we report the synthesis of solid organics under ionizing conditions in a plasma setup from gas mixtures (H2(O)−CO−N2−noble gases) reminiscent of the protosolar nebula composition. Ionization of the gas phase was achieved at temperatures up to 1,000 K. Synthesized solid compounds share chemical and structural features with chondritic organics, and noble gases trapped during the experiments reproduce the elemental and isotopic fractionations observed in primitive organics. These results strongly suggest that both the formation of chondritic refractory organics and the trapping of noble gases took place simultaneously in the ionized areas of the protoplanetary disk, via photon- and/or electron-driven reactions and processing. Thus, synthesis of primitive organics might not have required a cold environment and could have occurred anywhere the disk is ionized, including in its warm regions. This scenario also supports N2 photodissociation as the cause of the large nitrogen isotopic range in the solar system. PMID:26039983

Modern Electrochemical Aspects for the Synthesis of Value-Added Organic Products.

PubMed

Möhle, Sabine; Zirbes, Michael; Rodrigo, Eduardo; Gieshoff, Tile; Wiebe, Anton; Waldvogel, Siegfried R

2018-05-22

The use of electricity instead of stoichiometric amounts of oxidizers or reducing agents in synthesis is very appealing for economic and ecological reasons, and represents a major driving force for research efforts in this area. To use electron transfer at the electrode for a successful transformation in organic synthesis, the intermediate radical (cation/anion) has to be stabilized. Its combination with other approaches in organic chemistry or concepts of contemporary synthesis allows the establishment of powerful synthetic methods. The aim in the 21st Century will be to use as little fossil carbon as possible and, for this reason, the use of renewable sources is becoming increasingly important. The direct conversion of renewables, which have previously mainly been incinerated, is of increasing interest. This Review surveys many of the recent seminal important developments which will determine the future of this dynamic emerging field. © 2018 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

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

ERIC Educational Resources Information Center

Mak, Kendrew K. W.

2004-01-01

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

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

PubMed Central

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

2016-01-01

Proton-coupled electron transfers (PCETs) are unconventional redox processes in which both protons and electrons are exchanged, often in a concerted elementary step. While PCET is now recognized to play a central a role in biological redox catalysis and inorganic energy conversion technologies, its applications in organic synthesis are only beginning to be explored. In this chapter we aim to highlight the origins, development and evolution of 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

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

ERIC Educational Resources Information Center

Marks, Patrick; Levine, Mindy

2012-01-01

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

"In silico" mechanistic studies as predictive tools in microwave-assisted organic synthesis.

PubMed

Rodriguez, A M; Prieto, P; de la Hoz, A; Díaz-Ortiz, A

2011-04-07

Computational calculations can be used as a predictive tool in Microwave-Assisted Organic Synthesis (MAOS). A DFT study on Intramolecular Diels-Alder reactions (IMDA) indicated that the activation energy of the reaction and the polarity of the stationary points are two fundamental parameters to determine "a priori" if a reaction can be improved by using microwave irradiation.

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

ERIC Educational Resources Information Center

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

2008-01-01

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

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

ERIC Educational Resources Information Center

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

2009-01-01

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

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

EPA Science Inventory

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...

A hydrogen fuel cell for rapid, enzyme-catalysed organic synthesis with continuous monitoring.

PubMed

Wan, Lei; Megarity, Clare F; Siritanaratkul, Bhavin; Armstrong, Fraser A

2018-01-23

A one-pot fuel cell for specific, enzyme-catalysed organic synthesis, with continuous monitoring of rate and reaction progress, combines an electrode catalysing rapid, reversible and diffusion-controlled interconversion of NADP + and NADPH with a Pt electrode catalysing 2H + /H 2 interconversion. This Communication demonstrates its performance and characteristics using the reductive amination of 2-oxoglutarate as a test system.

MICROWAVE EFFECTS IN ORGANIC SYNTHESIS: MECHANISTIC AND REACTION MEDIUM CONSIDERATIONS

EPA Science Inventory

The scope of applications of microwave irradiation relates to a wide spectrum of organic syntheses with numerous benefits (reduction in reaction times, improved purity of products and better yields) encompassing advantages of both thermal and (or) specific non-purely thermal effe...

Biodiesel Synthesis and Evaluation: An Organic Chemistry Experiment

ERIC Educational Resources Information Center

Bucholtz, Ehren C.

2007-01-01

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

Burnout and Organization in Education: A Synthesis of Literature.

ERIC Educational Resources Information Center

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…

ENVIRONMENTALLY FRIENDLIER ALTERNATIVES TO ORGANIC SYNTHESIS USING MICROWAVES

EPA Science Inventory

Microwave irradiation has been used for a variety of organic transformations wherein chemical reactions are expedited because of selective adsorption of microwave (MW) energy by polar molecules, non-polar molecules being inert to the MW dielectric loss. The MW application under s...

Abiotic regulation: a common way for proteins to modulate their functions.

PubMed

Zou, Zhi; Fu, Xinmiao

2015-01-01

Modulation of protein intrinsic activity in cells is generally carried out via a combination of four common ways, i.e., allosteric regulation, covalent modification, proteolytic cleavage and association of other regulatory proteins. Accumulated evidence indicate that changes of certain abiotic factors (e.g., temperature, pH, light and mechanical force) within or outside the cells directly influence protein structure and thus profoundly modulate the functions of a wide range of proteins, termed as abiotic regulatory proteins (e.g., heat shock factor, small heat shock protein, hemoglobin, zymogen, integrin, rhodopsin). Such abiotic regulation apparently differs from the four classic ways in perceiving and response to the signals. Importantly, it enables cells to directly and also immediately response to extracellular stimuli, thus facilitating the ability of organisms to resist against and adapt to the abiotic stress and thereby playing crucial roles in life evolution. Altogether, abiotic regulation may be considered as a common way for proteins to modulate their functions.

High-rate synthesis of Cu-BTC metal-organic frameworks.

PubMed

Kim, Ki-Joong; Li, Yong Jun; Kreider, Peter B; Chang, Chih-Hung; Wannenmacher, Nick; Thallapally, Praveen K; Ahn, Ho-Geun

2013-12-21

The reaction conditions for the synthesis of Cu-BTC (BTC = benzene-1,3,5-tricarboxylic acid) were elucidated using a continuous-flow microreactor-assisted solvothermal system to achieve crystal size and phase control. A high-rate synthesis of Cu-BTC metal-organic frameworks with a BET surface area of more than 1600 m(2) g(-1) (Langmuir surface area of more than 2000 m(2) g(-1)) and with a 97% production yield could be achieved with a total reaction time of 5 minutes.

Pew Memorial Trust policy synthesis: 5. State coverage for organ transplantation: a framework for decision making.

PubMed

Lindsey, P A; McGlynn, E A

1988-02-01

Transplantation of hearts and livers for both adults and children is increasingly viewed as therapeutic and lifesaving, but access to these procedures is impeded by their high cost as well as by a limited supply of organs. In the absence of comprehensive federal coverage, pressure is being brought to bear on states to provide broader access to these procedures. This synthesis provides a framework for the consideration of coverage decisions at the state level. While there are no "right" answers about whether a state should support such coverage, the analytic tools of cost analysis, demand estimation, and assessment of capacity described in this synthesis can better inform the decision-making process.

Experimental Investigation of Organic Synthesis in Hydrothermal Environments

NASA Technical Reports Server (NTRS)

Shock, Everett L.

1998-01-01

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. The experiments are being performed using the hydrothermal bomb apparatus at the U.S. Geological Survey in Menlo Park, CA and the supercritical water oxidizer (SCWO) at NASA Ames Research Center in Moffet Field, CA. The amino acids decomposed rapidly. Even after the approximately 15 minutes between addition of the amino acids and the first sampling, no amino acids were detected in the PPM system by GC- MS, while in the FeFeO system the amino acids were present at a level of less than 50% of original. Carboxylic acids, ammonia, and CO2 were the main products, along with some unidentified compounds. The ratios of carboxylic acids and concentrations of other products seem to have remained stable during the experiments, consistent with observations of other metastable systems and theoretical predictions.

Synthesis of Amino Acid Precursors with Organic Solids in Planetesimals with Liquid Water

NASA Technical Reports Server (NTRS)

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

2017-01-01

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

Synthesis and Mass Spectrometric Characterization of Organic Nitrates

NASA Astrophysics Data System (ADS)

Grünert, A.; Woidich, S.; Ballschmiter, K.

2003-04-01

Organic nitrates, as trace constituents in urban air, can be analyzed by adsorptive low volume sampling (LVS) as well as by adsorptive high volume sampling (HVS). Air samples ranging from 25 L to 100 L for the LVS and 100 m3 to 500 m3 for the (HVS) were collected, respectively. Analysis is performed by thermodesorption (LVS) or solvent elution combined with group separation (HVS) using normal-phase HPLC and high resolution capillary gas chromatography with electron capture detection (HRGC-ECD) and mass selective detection (HRGC-MSD). For identification and quantification available reference compounds are required for both methods (1;2). Following numbers of congeners of organic nitrate have been synthesized: 77 monoalkyl nitrates (C1-C16), 43 dialkyl nitrates (C2-C10), 37 hydroxy alkyl nitrates (C2-C8) and 41 carbonyl alkyl nitrates (C3-C12). Alkanes, alkenes, alcohols, ketones and halocarbons have been used as precursors. Characterisation of the reference compounds by retention-data and mass-spectra was performed by high resolution capillary gas chromatography with mass selective detection in the EI- and the NCI (CH4) mode (1-3). EI-ionization leads to the dominating indicator ion NO2+ for organic nitrates with m/z = 46 u. The characteristic fragments with NCI (CH4) show ions at m/z = 46 u and m/z = 62 u, corresponding to NO2- and NO3-. The use of flame ionisation detection (HRGC-FID) and the principle of the molar response for carbon allows the quantitation of reference solutions as the final tool for the determination of the levels and patterns of organic nitrates in urban air samples. (1) J. Kastler: "Analytik, Massenspektrometrie und Vorkommen multifunktioneller Alkylnitrate in belasteter und unbelasteter Atmosphäre" Dr.rer.nat.-Thesis, University of Ulm (1999) (2) G. Werner, J. Kastler, R. Looser, K. Ballschmiter: "Organic Nitrates of Isoprenes as Atmospheric Trace Compounds" Angew. Chem. Int. Ed. (1999) 38(11): 1634-1637 (3) S.Woidich, O. Froscheis, O

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

NASA Technical Reports Server (NTRS)

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

1972-01-01

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

Integrated production of fuel gas and oxygenated organic compounds from synthesis gas

DOEpatents

Moore, Robert B.; Hegarty, William P.; Studer, David W.; Tirados, Edward J.

1995-01-01

An oxygenated organic liquid product and a fuel gas are produced from a portion of synthesis gas comprising hydrogen, carbon monoxide, carbon dioxide, and sulfur-containing compounds in a integrated feed treatment and catalytic reaction system. To prevent catalyst poisoning, the sulfur-containing compounds in the reactor feed are absorbed in a liquid comprising the reactor product, and the resulting sulfur-containing liquid is regenerated by stripping with untreated synthesis gas from the reactor. Stripping offgas is combined with the remaining synthesis gas to provide a fuel gas product. A portion of the regenerated liquid is used as makeup to the absorber and the remainder is withdrawn as a liquid product. The method is particularly useful for integration with a combined cycle coal gasification system utilizing a gas turbine for electric power generation.

Design and synthesis of an exceptionally stable and highly porous metal-organic framework

NASA Astrophysics Data System (ADS)

Li, Hailian; Eddaoudi, Mohamed; O'Keeffe, M.; Yaghi, O. M.

1999-11-01

Open metal-organic frameworks are widely regarded as promising materials for applications in catalysis, separation, gas storage and molecular recognition. Compared to conventionally used microporous inorganic materials such as zeolites, these organic structures have the potential for more flexible rational design, through control of the architecture and functionalization of the pores. So far, the inability of these open frameworks to support permanent porosity and to avoid collapsing in the absence of guest molecules, such as solvents, has hindered further progress in the field. Here we report the synthesis of a metal-organic framework which remains crystalline, as evidenced by X-ray single-crystal analyses, and stable when fully desolvated and when heated up to 300°C. This synthesis is achieved by borrowing ideas from metal carboxylate cluster chemistry, where an organic dicarboxylate linker is used in a reaction that gives supertetrahedron clusters when capped with monocarboxylates. The rigid and divergent character of the added linker allows the articulation of the clusters into a three-dimensional framework resulting in a structure with higher apparent surface area and pore volume than most porous crystalline zeolites. This simple and potentially universal design strategy is currently being pursued in the synthesis of new phases and composites, and for gas-storage applications.

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

PubMed

Kathiresan, Murugavel; Velayutham, David

2015-12-25

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

Trophic magnification of organic chemicals: A global synthesis

USGS Publications Warehouse

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

2016-01-01

Production of organic chemicals (OCs) is increasing exponentially, and some OCs biomagnify through food webs to potentially toxic levels. Biomagnification under field conditions is best described by trophic magnification factors (TMFs; per trophic level change in log-concentration of a chemical) which have been measured for more than two decades. Syntheses of TMF behavior relative to chemical traits and ecosystem properties are lacking. We analyzed >1500 TMFs to identify OCs predisposed to biomagnify and to assess ecosystem vulnerability. The highest TMFs were for OCs that are slowly metabolized by animals (metabolic rate kM < 0.01 day–1) and are moderately hydrophobic (log KOW 6–8). TMFs were more variable in marine than freshwaters, unrelated to latitude, and highest in food webs containing endotherms. We modeled the probability that any OC would biomagnify as a combined function of KOW and kM. Probability is greatest (∼100%) for slowly metabolized compounds, regardless of KOW, and lowest for chemicals with rapid transformation rates (kM > 0.2 day–1). This probabilistic model provides a new global tool for screening existing and new OCs for their biomagnification potential.

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

SciTech Connect

Wang, Timothy C.; Vermeulen, Nicolaas A.; Kim, In Soo

The synthesis of NU-1000, a mesoporous metal-organic framework (MOF), can be conducted efficiently on a multigram scale from inexpensive starting materials. NU-1000 has been reported as an excellent candidate for gas separation and catalysis. In particular, it is ideal for the catalytic deactivation of nerve agents and shows great promise as a new generic platform for a wide range of applications. Multiple post-synthetic modification protocols have been developed using NU-1000 as the parent material, making it a potentially useful scaffold for several catalytic applications. The procedure for the preparation of NU-1000 can be scaled up reliably, and it is suitablemore » for the production of 50 g of the tetracarboxylic acid containing organic linker and 200 mg–2.5 g of NU-1000. Lastly, the entire synthesis is performed without purification by column chromatography and can be completed within 10 d.« less

An improved synthesis of pentacene: rapid access to a benchmark organic semiconductor.

PubMed

Pramanik, Chandrani; Miller, Glen P

2012-04-20

Pentacene is an organic semiconductor used in a variety of thin-film organic electronic devices. Although at least six separate syntheses of pentacene are known (two from dihydropentacenes, two from 6,13-pentacenedione and two from 6,13-dihydro-6,13-dihydroxypentacene), none is ideal and several utilize elevated temperatures that may facilitate the oxidation of pentacene as it is produced. Here, we present a fast (-2 min of reaction time), simple, high-yielding (≥ 90%), low temperature synthesis of pentacene from readily available 6,13-dihydro-6,13-dihydroxypentacene. Further, we discuss the mechanism of this highly efficient reaction. With this improved synthesis, researchers gain rapid, affordable access to high purity pentacene in excellent yield and without the need for a time consuming sublimation.

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

DOE PAGES

Wang, Timothy C.; Vermeulen, Nicolaas A.; Kim, In Soo; ...

2015-12-17

The synthesis of NU-1000, a mesoporous metal-organic framework (MOF), can be conducted efficiently on a multigram scale from inexpensive starting materials. NU-1000 has been reported as an excellent candidate for gas separation and catalysis. In particular, it is ideal for the catalytic deactivation of nerve agents and shows great promise as a new generic platform for a wide range of applications. Multiple post-synthetic modification protocols have been developed using NU-1000 as the parent material, making it a potentially useful scaffold for several catalytic applications. The procedure for the preparation of NU-1000 can be scaled up reliably, and it is suitablemore » for the production of 50 g of the tetracarboxylic acid containing organic linker and 200 mg–2.5 g of NU-1000. Lastly, the entire synthesis is performed without purification by column chromatography and can be completed within 10 d.« less

The mammalian iris-ciliary complex affects organization and synthesis of cytoskeletal proteins of organ and tissue cultured lens epithelial cells.

PubMed

Banerjee, A; Emanuel, K; Parafina, J; Bagchi, M

1992-10-01

A water soluble growth inhibitor was isolated from the mammalian ocular iris-ciliary complex. The molecular weight of this protein is 10 kD or lower as determined by ultrafiltration fractionation. The iris-ciliary (IC) complex water soluble protein(s) significantly inhibits synthesis of lower molecular weight proteins of the epithelial cells of the organ cultured mammalian ocular lens. It was also found that this inhibitory effect of IC is mediated via the structural organization of the lens. Monolayer cultures of the lens epithelial cells exposed to IC did not manifest any inhibition of their protein synthesis. Moreover, these tissue cultured lens epithelial (TCLE) cells showed a significant increase in their protein synthetic activities in response to the presence of IC factors in the culture medium. It is postulated that the IC activity is modulated via either the lens capsule, an extracellular matrix, or due to the specific organization of the intact lens. The specific effects of IC on the cytoskeletal organization and synthesis in the organ cultured lens epithelial (OCLE) and TCLE cells were also examined. Both groups, treated with IC factors, manifested significant alterations in their protein synthetic activities and cytoskeletal architecture. The 3H-leucine incorporation experiments showed that alpha-actin and alpha-tubulin synthesis is partially inhibited by IC factors in OCLE cells but vimentin synthesis is not, whereas in TCLE cells all of them showed increased synthesis in response to IC factors. Turnover rates of these proteins in both OCLE and TCLE cells were also computed. The immunofluorescence and microscopic evaluation of OCLE and TCLE cells exposed to IC factors illustrated significant alteration in the cytoarchitecture of the filaments. We demonstrate that an inhibitor(s) molecule of 10 kD or lower size isolated from IC inhibited protein synthesis of OCLE cells and stimulated protein synthesis in TCLE cells. The IC factor also affects the

Perspective: Whither the problem list? Organ-based documentation and deficient synthesis by medical trainees.

PubMed

Kaplan, Daniel M

2010-10-01

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.

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

ERIC Educational Resources Information Center

Yokus, Hamit; Yokus, Tuba

2015-01-01

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

Synthesis of New Organic Semiconducting Polymer Materials Having High Radiowave Absorption Rate

DTIC Science & Technology

2008-11-01

ISTC Project No. #1571P Synthesis of New Organic Semiconducting Polymer Materials Having High Radiowave Absorption Rate Final Project Technical...Technology Center ( ISTC ), Moscow. REPORT DOCUMENTATION PAGE Form Approved OMB No. 0704-0188 Public reporting burden for this collection of information...polymer materials having high radiowave absorption rate 5a. CONTRACT NUMBER ISTC Registration No: A-1571p 5b. GRANT NUMBER 5c. PROGRAM ELEMENT

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

ERIC Educational Resources Information Center

Marchetti, Louis; DeBoef, Brenton

2015-01-01

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

Benefits of Using a Problem-Solving Scaffold for Teaching and Learning Synthesis in Undergraduate Organic Chemistry I

ERIC Educational Resources Information Center

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

2016-01-01

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…

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

ERIC Educational Resources Information Center

Andraos, John

2015-01-01

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

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

PubMed

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

2014-08-07

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

Chemoenzymatic Synthesis of an Enantiomerically Pure Lactone: A Three-Step Synthesis for Undergraduate Organic Chemistry Laboratory

NASA Astrophysics Data System (ADS)

McClure, Cynthia K.; Chenault, H. Keith

1996-05-01

A three-step laboratory sequence for the undergraduate organic laboratory is described. This series of experiments requires a student to use the product from one reaction as the starting material for a subsequent reaction, and thus the affords the student a "real world" experience of multistep synthesis. Thermal extrusion of sulfur dioxide from sulfolene is used to generate 1,3-butadiene in situ for a Diels-Alder cyclization with maleic anhydride. The anhydride is then reduced to the diol with lithium aluminum hydride. Oxidation of the diol to the chiral lactone is catalyzed by horse-liver alcohol dehydrogenase. This enzymatic oxidation illustrates in situ cofactor regeneration and allows students to measure simple enzyme kinetics.

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

SciTech Connect

Panchal, Chandrakant B; Prindle, John C; Kolah, Aspri

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.

Synthesis and morphogenesis of organic polymer materials with hierarchical structures in biominerals.

PubMed

Oaki, Yuya; Kijima, Misako; Imai, Hiroaki

2011-06-08

Synthesis and morphogenesis of polypyrrole (PPy) with hierarchical structures from nanoscopic to macroscopic scales have been achieved by using hierarchically organized architectures of biominerals. We adopted biominerals, such as a sea urchin spine and nacreous layer, having hierarchical architectures based on mesocrystals as model materials used for synthesis of an organic polymer. A sea urchin spine led to the formation of PPy macroscopic sponge structures consisting of nanosheets less than 100 nm in thickness with the mosaic interior of the nanoparticles. The morphologies of the resultant PPy hierarchical architectures can be tuned by the structural modification of the original biomineral with chemical and thermal treatments. In another case, a nacreous layer provided PPy porous nanosheets consisting of the nanoparticles. Conductive pathways were formed in these PPy hierarchical architectures. The nanoscale interspaces in the mesocrystal structures of biominerals are used for introduction and polymerization of the monomers, leading to the formation of hierarchically organized polymer architectures. These results show that functional organic materials with complex and nanoscale morphologies can be synthesized by using hierarchically organized architectures as observed in biominerals.

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

ERIC Educational Resources Information Center

Overstreet, Kirk E., Jr.

2017-01-01

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…

Abiotic degradation of plastic films

NASA Astrophysics Data System (ADS)

Ángeles-López, Y. G.; Gutiérrez-Mayen, A. M.; Velasco-Pérez, M.; Beltrán-Villavicencio, M.; Vázquez-Morillas, A.; Cano-Blanco, M.

2017-01-01

Degradable plastics have been promoted as an option to mitigate the environmental impacts of plastic waste. However, there is no certainty about its degradability under different environmental conditions. The effect of accelerated weathering (AW), natural weathering (NW) and thermal oxidation (TO) on different plastics (high density polyethylene, HDPE; oxodegradable high density polyethylene, HDPE-oxo; compostable plastic, Ecovio ® metalized polypropylene, PP; and oxodegradable metalized polypropylene, PP-oxo) was studied. Plastics films were exposed to AW per 110 hours; to NW per 90 days; and to TO per 30 days. Plastic films exposed to AW and NW showed a general loss on mechanical properties. The highest reduction in elongation at break on AW occurred to HDPE-oxo (from 400.4% to 20.9%) and was higher than 90% for HDPE, HDPE-oxo, Ecovio ® and PP-oxo in NW. No substantial evidence of degradation was found on plastics exposed to TO. Oxo-plastics showed higher degradation rates than their conventional counterparts, and the compostable plastic was resistant to degradation in the studied abiotic conditions. This study shows that degradation of plastics in real life conditions will vary depending in both, their composition and the environment.

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

PubMed Central

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

2014-01-01

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

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

PubMed

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

2014-10-28

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

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

NASA Technical Reports Server (NTRS)

Simoneit, Bernd R. T.

1995-01-01

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

New 2D Carbon Nitride Organic Materials Synthesis with Huge-Application Prospects in CN Photocatalyst.

PubMed

Zhao, Gang; Cheng, Yanling; Wu, Yongzhong; Xu, Xijin; Hao, Xiaopeng

2018-04-01

In recent years, 2D materials are attracting increased attention because of their excellent properties. In this paper, new 2D carbon nitride (CN) organic materials are successfully prepared on the basis of the organic synthesis theory, and the thickness is about 1.5 nm. This new 2D CN organic material further strengthens the 2D materials family. Meanwhile, their synthetic mechanism is theoretically speculated. Then CN photocatalysts of several structures are obtained by roasting 2D CN organic materials. Through the photocatalytic hydrogen production experiments, the results exhibit that these kinds of photocatalysts have good photocatalytic effects compared to common g-C 3 N 4 . © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Abiotic controls on N2O emissions from soils and wetlands

NASA Astrophysics Data System (ADS)

Horwath, W. R.

2016-12-01

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.

Soil heterogeneity in Mojave Desert shrublands: Biotic and abiotic processes

NASA Astrophysics Data System (ADS)

Caldwell, Todd G.; Young, Michael H.; McDonald, Eric V.; Zhu, Jianting

2012-09-01

Geological and ecological processes play critical roles in the evolution of desert piedmonts. Feedback between fast cyclic biotic and slow cumulative pedogenic processes on arid alluvial fan systems results in a heterogeneous landscape of interspace and canopy microsites. Defining the spatial extent between these processes will allow a better connection to ecosystem service and climate change. We use a soil chronosequence in the Mojave Desert and high spatial resolution infiltrometer measurements along transects radiating from canopies of perennial shrubs to assess the extent of biotic and abiotic processes and the heterogeneity of soil properties in arid shrublands. Results showed higher saturated conductivity under vegetation regardless of surface age, but it was more conspicuous on older, developed soils. At proximal locations to the shrub, bulk density, soil structure grade, silt, and clay content significantly increased radially from the canopy, while sand and organic material decreased. Soil properties at distal locations 2-5 times the canopy radius had no significant spatial correlation. The extent of the biotic influence of the shrub was 1.34 ± 0.32 times the canopy radius. Hydraulic properties were weakly correlated in space, but 75% of the variance could be attributed to sand content, soil structure grade, mean-particle diameter, and soil organic material, none of which are exclusively biotic or abiotic. The fast cyclic biotic processes occurring under vegetation are clearly overprinted on slow cumulative abiotic processes, resulting in the deterministic variability observed at the plant scale.

Arbuscular mycorrhizal fungal responses to abiotic stresses: A review.

PubMed

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

2016-03-01

The majority of plants live in close collaboration with a diversity of soil organisms among which arbuscular mycorrhizal fungi (AMF) play an essential role. Mycorrhizal symbioses contribute to plant growth and plant protection against various environmental stresses. Whereas the resistance mechanisms induced in mycorrhizal plants after exposure to abiotic stresses, such as drought, salinity and pollution, are well documented, the knowledge about the stress tolerance mechanisms implemented by the AMF themselves is limited. This review provides an overview of the impacts of various abiotic stresses (pollution, salinity, drought, extreme temperatures, CO2, calcareous, acidity) on biodiversity, abundance and development of AMF and examines the morphological, biochemical and molecular mechanisms implemented by AMF to survive in the presence of these stresses. Copyright © 2016 Elsevier Ltd. All rights reserved.

Marine invertebrates, model organisms, and the modern synthesis: epistemic values, evo-devo, and exclusion.

PubMed

Love, Alan C

2009-03-01

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.

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

PubMed

Vaid, Thomas P; Kelley, Steven P; Rogers, Robin D

2017-07-01

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.

Iron Containing Metal-Organic Frameworks: Structure, Synthesis, and Applications in Environmental Remediation.

PubMed

Liu, Xiaocheng; Zhou, Yaoyu; Zhang, Jiachao; Tang, Lin; Luo, Lin; Zeng, Guangming

2017-06-21

Metal-organic frameworks (MOFs) with Fe content are gradually developing into an independent branch in environmental remediation, requiring economical, effective, low-toxicity strategies to the complete procedure. In this review, recent advancements in the structure, synthesis, and environmental application focusing on the mechanism are presented. The unique structure of novel design proposed specific characteristics of different iron-containing MOFs with potential innovation. Synthesis of typical MILs, NH 2 -MILs and MILs based materials reveal the basis and defect of the current method, indicating the optimal means for the actual requirements. The adsorption of various contamination with multiple interaction as well as the catalytic degradation over radicals or electron-hole pairs are reviewed. This review implied considerable prospects of iron-containing MOFs in the field of environment and a more comprehensive cognition into the challenges and potential improvement.

Chemical oxidative and solid state synthesis of low molecular weight polymers for organic field effect transistors

NASA Astrophysics Data System (ADS)

Mahale, Rajashree Y.; Dharmapurikar, Satej S.; Chini, Mrinmoy Kumar

2018-03-01

Solution processability of the precursor molecules is a major issue owing to their limited solubility for the synthesis of conjugated polymers. Therefore, we favour the solvent free solid state chemical oxidative polymerization route for the synthesis of diketopyrrolopyrrole (DPP) based donor-acceptor (D-A) type conjugated polymers. D-A type polymer Poly(S-OD-EDOT) which contains DPP coupled with EDOT donor units is synthesized via solid state polymerization method. The polymer is employed as an active layer for organic field-effect transistors to measure charge transport properties. The Polymer shows good hole mobility 3.1 × 10-2 cm2 V-1 s-1, with a on/off ratio of 1.1 × 103.

Energy Utilization for Polysaccharide Synthesis by Mixed Rumen Organisms Fermenting Soluble Carbohydrates

PubMed Central

Walker, D. J.

1968-01-01

Synthesis of reserve polysaccharide by mixed rumen organisms fermenting glucose, maltose, cellobiose, and xylose has been studied in relation to the adenosine triphosphate energy calculated to be available from substrate fermentation. About 80% of the energy available from glucose and xylose was used for polysaccharide synthesis, whereas, assuming hydrolytic cleavage of the disaccharides, more than 100% was used when cellobiose and maltose were the substrates. If, however, phosphorolytic cleavage of the disaccharides, for which there is evidence, was involved, the energy from both maltose and cellobiose fermentation was used with about the same efficiency as that from glucose and xylose fermentation. The rumen fluid used was collected 24 hr after feeding, and growth of microorganisms in such samples was sufficient to account for utilization of less than 10% of the total energy becoming available during the 40-min incubation period. PMID:16349819

[Intensity of DNA synthesis in animal organs after a flight on the Kosmos-782 biosatellite].

PubMed

Guseĭnov, F T; Egorov, I A; Komolova, G S; Tigranian, R A

1979-01-01

With respect to H3-thymidine incorporation the rate of DNA synthesis in the liver, spleen and thymus of rats was determined in flight and synchronous rats. Six hours post-flight the rate of H3-thymidine incorporation into the liver of flight rats did not differ from the normal (vivarium controls) and was 50% higher than in the synchronous rats. In the spleen and thymus of flight animals this parameter was 60 and 33% below the norm. Similar but less pronounced changes in the spleen were found in the synchronous rats. Twenty-five days postflight the rate of DNA synthesis in lymph organs recovered completely and tended to increase, whereas in the liver it remained significantly below the norm.

Influence of trimetazidine on the synthesis of complex lipids in the heart and other target organs

NASA Technical Reports Server (NTRS)

Sentex, E.; Helies-Toussaint, C.; Rousseau, D.; Lucien, A.; Ferrary, E.; Grynberg, A.

2001-01-01

Trimetazidine exerts antianginal properties at the cellular level, without haemodynamic effect in clinical and experimental conditions. This cytoprotection was attributed to a decreased utilization of fatty acids for energy production, balanced by an increased incorporation in structural lipids. This study evaluated the influence of Trimetazidine on complex lipid synthesis from [2-(3)H] glycerol, in ventricular myocytes, isolated rat hearts and in vivo in the myocardium and several other tissues. In cardiomyocytes, Trimetazidine increased the synthesis of phosphatidyl-choline (+ 80%), phosphatidyl-ethanolamine (+ 210%), phosphatidyl-inositol (+ 250%) and cardiolipid (+ 100%). The common precursor diacylglycerol was also increased (+ 40%) whereas triacylglycerol was decreased (-70%). Similar results were obtained in isolated hearts with 10 microm Trimetazidine (phosphatidyl-choline + 60%, phosphatidyl-ethanolamine + 60%, phosphatidyl-inositol + 100% and cardiolipid + 50%), the last two phospholipids containing 85% of the radioactivity. At 1 microm, Trimetazidine still stimulated the phospholipid synthesis although the difference was found significant only in phosphatidyl-inositol and cardiolipid. In vivo studies (10 mg/kg per day for 7 days and 5 mg/kg, i.p. before the experiment) revealed significant changes in the intracellular lipid biosynthesis, with increased labelling of phospholipids and reduced incorporation of glycerol in nonphosphorous lipids. Trimetazidine increased the glycerol uptake from plasma to the other tissues (liver, cochlea, retina), resulting in an altered lipid synthesis. The anti-anginal properties of Trimetazidine involve a reorganisation of the glycerol-based lipid synthesis balance in cardiomyocytes, associated with an increased uptake of plasma glycerol that may contribute to explain the pharmacological properties reported in other organs.

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

ERIC Educational Resources Information Center

Martin, Eric; Kellen-Yuen, Cynthia

2007-01-01

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

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

PubMed Central

2014-01-01

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

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

PubMed

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

2014-01-14

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

Stomatal Complex Development and F-Actin Organization in Maize Leaf Epidermis Depend on Cellulose Synthesis.

PubMed

Panteris, Emmanuel; Achlati, Theonymphi; Daras, Gerasimos; Rigas, Stamatis

2018-06-06

Cellulose microfibrils reinforce the cell wall for morphogenesis in plants. Herein, we provide evidence on a series of defects regarding stomatal complex development and F-actin organization in Zea mays leaf epidermis, due to inhibition of cellulose synthesis. Formative cell divisions of stomatal complex ontogenesis were delayed or inhibited, resulting in lack of subsidiary cells and frequently in unicellular stomata, with an atypical stomatal pore. Guard cells failed to acquire a dumbbell shape, becoming rounded, while subsidiary cells, whenever present, exhibited aberrant morphogenesis. F-actin organization was also affected, since the stomatal complex-specific arrays were scarcely observed. At late developmental stages, the overall F-actin network was diminished in all epidermal cells, although thick actin bundles persisted. Taken together, stomatal complex development strongly depends on cell wall mechanical properties. Moreover, F-actin organization exhibits a tight relationship with the cell wall.

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

PubMed

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

2016-01-01

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

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

SciTech Connect

Wang, Timothy C.; Vermeulen, Nicolaas A.; Kim, In Soo

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

Advances in Electrocatalysis for Energy Conversion and Synthesis of Organic Molecules.

PubMed

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

2017-10-06

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.

Synthesis of Zeolites Using the ADOR (Assembly-Disassembly-Organization-Reassembly) Route

PubMed Central

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

2016-01-01

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. PMID:27078165

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

PubMed

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

2016-04-03

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.

Titania may produce abiotic oxygen atmospheres on habitable exoplanets

PubMed Central

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

2015-01-01

The search for habitable exoplanets in the Universe is actively ongoing in the field of astronomy. The biggest future milestone is to determine whether life exists on such habitable exoplanets. In that context, oxygen in the atmosphere has been considered strong evidence for the presence of photosynthetic organisms. In this paper, we show that a previously unconsidered photochemical mechanism by titanium (IV) oxide (titania) can produce abiotic oxygen from liquid water under near ultraviolet (NUV) lights on the surface of exoplanets. Titania works as a photocatalyst to dissociate liquid water in this process. This mechanism offers a different source of a possibility of abiotic oxygen in atmospheres of exoplanets from previously considered photodissociation of water vapor in upper atmospheres by extreme ultraviolet (XUV) light. Our order-of-magnitude estimation shows that possible amounts of oxygen produced by this abiotic mechanism can be comparable with or even more than that in the atmosphere of the current 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. PMID:26354078

Titania may produce abiotic oxygen atmospheres on habitable exoplanets.

PubMed

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

2015-09-10

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.

Induction of abiotic stress tolerance in plants by endophytic microbes.

PubMed

Lata, R; Chowdhury, S; Gond, S K; White, J F

2018-04-01

Endophytes are micro-organisms including bacteria and fungi that survive within healthy plant tissues and promote plant growth under stress. This review focuses on the potential of endophytic microbes that induce abiotic stress tolerance in plants. How endophytes promote plant growth under stressful conditions, like drought and heat, high salinity and poor nutrient availability will be discussed. The molecular mechanisms for increasing stress tolerance in plants by endophytes include induction of plant stress genes as well as biomolecules like reactive oxygen species scavengers. This review may help in the development of biotechnological applications of endophytic microbes in plant growth promotion and crop improvement under abiotic stress conditions. Increasing human populations demand more crop yield for food security while crop production is adversely affected by abiotic stresses like drought, salinity and high temperature. Development of stress tolerance in plants is a strategy to cope with the negative effects of adverse environmental conditions. Endophytes are well recognized for plant growth promotion and production of natural compounds. The property of endophytes to induce stress tolerance in plants can be applied to increase crop yields. With this review, we intend to promote application of endophytes in biotechnology and genetic engineering for the development of stress-tolerant plants. © 2018 The Society for Applied Microbiology.

Epoxidation of Geraniol: An Advanced Organic Experiment that Illustrates Asymmetric Synthesis

NASA Astrophysics Data System (ADS)

Bradley, Lynn M.; Springer, Joseph W.; Delate, Gregory M.; Goodman, Andrew

1997-11-01

The Sharpless epoxidation reaction is considered one of the most powerful advances in asymmetric organic synthesis (1). It is a classic example of the use of an asymmetric catalyst to provide an enantiomerically enriched mixture of epoxy alcohols. The procedure typically uses titanium(IV) tetraisopropoxide (Ti(OiPr)4) as a catalyst, a peroxide, and dialkyl tartrates to induce asymmetry in the epoxidation reaction of allylic alcohols. The experiment described in this paper illustrates the principle of asymmetric epoxidation and enables students to determine enantiomeric product ratios using chiral shift reagents and NMR spectroscopy.

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

DOEpatents

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

2017-03-21

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.

In-hospital experiences of families of potential organ donors: A systematic review and qualitative synthesis

PubMed Central

Dicks, Sean Glenton; Ranse, Kristen; van Haren, Frank MP; Boer, Douglas P

2017-01-01

Information and compassion assist families of potential organ donors to make informed decisions. However, psychological implications of the in-hospital process are not well described with past research focusing on decision-making. To enhance understanding and improve service delivery, a systematic review was conducted. Inductive analysis and synthesis utilised Grounded Theory Methodology within a systems theory framework and contributed to a model proposing that family and staff form a System of Systems with shared responsibility for process outcomes. This model can guide evaluation and improvement of care and will be tested by means of a longitudinal study of family experiences. PMID:28680696

Low-energy N+ ion irradiation induced synthesis of nitrogenous compound from solid organic sodium salts

NASA Astrophysics Data System (ADS)

Wang, Xiangqin; Yu, Zengliang

2003-08-01

In this paper, samples of solid organic sodium salts (sodium formate, sodium acetate and sodium benzoate) were irradiated by low-energy N+ ions. The induced damage was detected by infrared (FT-IR). It is shown that a new cyano group (-CN) and amino group (-NH2) were formed in the irradiated sodium carbroxylic sample with N+ ion irradiation. The experimental results examined the effect of N+ ion irradiation by reacting with sodium salt molecules, and presented a new way for the synthesis of nitrogenous compound by low-energy ion irradiation.

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

PubMed

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

2016-09-14

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

Synthesis and characterization of organic-inorganic polymers from new methacrylate monomers and silane derivatives

NASA Astrophysics Data System (ADS)

Nicolescu, F. Adriana; Jerca, Victor V.; Albu, Ana M.; Vasilescu, D. Sorin; Vuluga, D. Mircea

2009-09-01

We report the synthesis of five new hybrid polymeric structures obtained by free radical copolymerization of some organic azo-based methacrylate monomers and 3-methacryloxypropyl trimethoxysilane (MEMO). The copolymers are soluble in common solvents like methylene chloride, chloroform, dichlorbenzene, dimethylsulfoxide, dimethylformamide. The copolymeric structures might be interesting from the point of view of nonlinear optical response due to a rich content in chromophoric units determined by H-NMR spectroscopy. The structures were also characterized by FT-IR spectroscopy, TGA and SEC analysis.

Zeolite-like metal–organic frameworks (ZMOFs): Design, synthesis, and properties

DOE PAGES

Eddaoudi, Mohamed; Sava, Dorina F.; Eubank, Jarrod F.; ...

2015-10-24

This study 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 properties towards specific applications.

Carbohydrates protect protein against abiotic fragmentation by soil minerals

SciTech Connect

Reardon, Patrick N.; Walter, Eric D.; Marean-Reardon, Carrie L.

The degradation and turnover of soil organic matter is an important part of global carbon cycling and of particular importance with respect to attempts to predict the response of ecosystems to global climate change. Thus, it is important to mechanistically understand the processes by which organic matter can be degraded in the soil environment, including contact with reactive or catalytic mineral surfaces. We have characterized the outcome of the interaction of two minerals, birnessite and kaolinite, with two disaccharides, cellobiose and trehalose. These results show that birnessite reacts with and degrades the carbohydrates, while kaolinite does not. The reaction ofmore » disaccharides with birnessite produces Mn(II), indicating that degradation of the disaccharides is the result of their oxidation by birnessite. Furthermore, we find that both sugars can inhibit the degradation of a model protein by birnessite, demonstrating that the presence of one organic constituent can impact abiotic degradation of another. Therefore, both the reactivity of the mineral matrix and the presence of certain organic constituents influence the outcomes of abiotic degradation. These results suggest the possibility that microorganisms may be able to control the functionality of exoenzymes through the concomitant excretion of protective organic substances, such as those found in biofilms.« less

Arctic Synthesis Collaboratory: A Virtual Organization for Transformative Research and Education on a Changing Arctic

NASA Astrophysics Data System (ADS)

Warnick, W. K.; Wiggins, H. V.; Hinzman, L.; Holland, M.; Murray, M. S.; Vörösmarty, C.; Loring, A. J.

2008-12-01

About the Arctic Synthesis Collaboratory The Arctic Synthesis Collaboratory concept, developed through a series of NSF-funded workshops and town hall meetings, is envisioned as a cyber-enabled, technical, organizational, and social-synthesis framework to foster: • Interactions among interdisciplinary experts and stakeholders • Integrated data analysis and modeling activities • Training and development of the arctic science community • Delivery of outreach, education, and policy-relevant resources Scientific Rationale The rapid rate of arctic change and our incomplete understanding of the arctic system present the arctic community with a grand scientific challenge and three related issues. First, a wealth of observations now exists as disconnected data holdings, which must be coordinated and synthesized to fully detect and assess arctic change. Second, despite great strides in the development of arctic system simulations, we still have incomplete capabilities for modeling and predicting the behavior of the system as a whole. Third, policy-makers, stakeholders, and the public are increasingly making demands of the science community for forecasts and guidance in mitigation and adaptation strategies. Collaboratory Components The Arctic Synthesis Collaboratory is organized around four integrated functions that will be established virtually as a distributed set of activities, but also with the advantage of existing facilities that could sponsor some of the identified activities. Community Network "Meeting Grounds:" The Collaboratory will link distributed individuals, organizations, and activities to enable collaboration and foster new research initiatives. Specific activities could include: an expert directory, social networking services, and virtual and face-to-face meetings. Data Integration, Synthesis, and Modeling Activities: The Collaboratory will utilize appropriate tools to enable the combination of data and models. Specific activities could include: a web

Saccharin Derivative Synthesis via [1,3] Thermal Sigmatropic Rearrangement: A Multistep Organic Chemistry Experiment for Undergraduate Students

ERIC Educational Resources Information Center

Fonseca, Custódia S. C.

2016-01-01

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…

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

ERIC Educational Resources Information Center

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

2014-01-01

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

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

EPA Science Inventory

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

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

NASA Astrophysics Data System (ADS)

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

2015-07-01

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

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

PubMed Central

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

2015-01-01

A novel, simple and efficient strategy for fabricating a magnetic metal-organic framework (MOF) as sorbent to remove organic compounds from simulated water samples is presented and tested for removal of methylene blue (MB) as an example. The novel adsorbents combine advantages of MOFs and magnetic nanoparticles and possess large capacity, low cost, rapid removal and easy separation of the solid phase, which makes it an excellent sorbent for treatment of wastewaters. The resulting magnetic MOFs composites (also known as MFCs) have large surface areas (79.52 m2 g−1), excellent magnetic response (14.89 emu g−1), and large mesopore volume (0.09 cm3 g−1), as well as good chemical inertness and mechanical stability. Adsorption was not drastically affected by pH, suggesting π–π stacking interaction and/or hydrophobic interactions between MB and MFCs. Kinetic parameters followed pseudo-second-order kinetics and adsorption was described by the Freundlich isotherm. Adsorption capacity was 84 mg MB g−1 at an initial MB concentration of 30 mg L−1, which increased to 245 mg g−1 when the initial MB concentration was 300 mg L−1. This capacity was much greater than most other adsorbents reported in the literature. In addition, MFC adsorbents possess excellent reusability, being effective after at least five consecutive cycles. PMID:26149818

Integration of Fermentation and Organic Synthesis: Studies of Roquefortine C and Biosynthetic Derivatives

NASA Astrophysics Data System (ADS)

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

Abiotic Stress Signaling in Wheat – An Inclusive Overview of Hormonal Interactions During Abiotic Stress Responses in Wheat

PubMed Central

Abhinandan, Kumar; Skori, Logan; Stanic, Matija; Hickerson, Neil M. N.; Jamshed, Muhammad; Samuel, Marcus A.

2018-01-01

Rapid global warming directly impacts agricultural productivity and poses a major challenge to the present-day agriculture. Recent climate change models predict severe losses in crop production worldwide due to the changing environment, and in wheat, this can be as large as 42 Mt/°C rise in temperature. Although wheat occupies the largest total harvested area (38.8%) among the cereals including rice and maize, its total productivity remains the lowest. The major production losses in wheat are caused more by abiotic stresses such as drought, salinity, and high temperature than by biotic insults. Thus, understanding the effects of these stresses becomes indispensable for wheat improvement programs which have depended mainly on the genetic variations present in the wheat genome through conventional breeding. Notably, recent biotechnological breakthroughs in the understanding of gene functions and access to whole genome sequences have opened new avenues for crop improvement. Despite the availability of such resources in wheat, progress is still limited to the understanding of the stress signaling mechanisms using model plants such as Arabidopsis, rice and Brachypodium and not directly using wheat as the model organism. This review presents an inclusive overview of the phenotypic and physiological changes in wheat due to various abiotic stresses followed by the current state of knowledge on the identified mechanisms of perception and signal transduction in wheat. Specifically, this review provides an in-depth analysis of different hormonal interactions and signaling observed during abiotic stress signaling in wheat. PMID:29942321

Synthesis of Inorganic-Organic Hybrid Materials Designed for Radiation Detection, Luminescence, and Gas Storage

NASA Astrophysics Data System (ADS)

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

Novelmetal-organic photocatalysts: Synthesis, characterization and decomposition of organic dyes

NASA Astrophysics Data System (ADS)

Gopal Reddy, N. B.; Murali Krishna, P.; Kottam, Nagaraju

2015-02-01

An efficient method for the photocatalytic degradation of methylene blue in an aqueous medium was developed using metal-organic complexes. Two novel complexes were synthesized using, Schiff base ligand, N‧-[(E)-(4-ethylphenyl)methylidene]-4-hydroxybenzohydrazide (HL) and Ni(II) (Complex 1)/Co(II) (Complex 2) chloride respectively. These complexes were characterized using microanalysis, various spectral techniques. Spectral studies reveal that the complexes exhibit square planar geometry with ligand coordination through azomethine nitrogen and enolic oxygen. The effects of catalyst dosage, irradiation time and aqueous pH on the photocatalytic activity were studied systematically. The photocatalytic activity was found to be more efficient in the presence of Ni(II) complexes than the Co(II) complex. Possible mechanistic aspects were discussed.

Synthesis and Characterization of Metal-Organic Frameworks (MOFs) That Are Difficult to Access De Novo

NASA Astrophysics Data System (ADS)

Karagiaridi, Olga

Metal-organic frameworks (MOFs) are a class of intriguing hybrid materials, comprised of metal-based nodes joined by organic linkers into a crystalline, porous, three-dimensional lattice. Their signature properties (well-defined surfaces, tailorability and ultra-high porosity) render them promising candidates for many applications, including, but not limited to, gas storage, gas separation, catalysis and sensing. One of the greatest challenges associated with MOF synthesis lies in the fact that obtaining a desired MOF structure that is tailored to perform a specific application is often not trivial. Traditional synthetic pathways termed "de novo synthesis" (typically one-pot reactions between the MOF structural building blocks under solvothermal conditions) often give rise to side products that do not possess the desired structure. To circumvent this problem, we have studied in depth two powerful MOF synthetic techniques -- solvent-assisted linker exchange (SALE) and transmetalation. These are heterogeneous reactions of parent MOF crystals with concentrated solutions of organic linkers and inorganic metal salts, respectively, that lead to the replacement of the linkers or metal nodes within the parent MOFs by the desired components, while the overall framework topology is preserved. The projects described in this dissertation have aimed to apply these techniques to transform simple (unfunctionalized) and easy to synthesize representative materials from various MOF systems to structurally and functionally interesting daughter products. Examples include synthesis of MOFs that are energetically "unfavorable", extension of MOF cages by longer linker incorporation, functionalization of MOF pores and endowment of MOFs with permanent and persistent porosity. Through these projects, we have been able to formulate a set of rules that can be applied to predict the successful outcome of SALE. Since the allure of MOFs lies in their applications, expanding the range of

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

PubMed

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

2017-10-31

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.

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

SciTech Connect

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 orbitalmore » energy level.« less

Silicon carbide passive heating elements in microwave-assisted organic synthesis.

PubMed

Kremsner, Jennifer M; Kappe, C Oliver

2006-06-09

Microwave-assisted organic synthesis in nonpolar solvents is investigated utilizing cylinders of sintered silicon carbide (SiC)--a chemically inert and strongly microwave absorbing material--as passive heating elements (PHEs). These heating inserts absorb microwave energy and subsequently transfer the generated thermal energy via conduction phenomena to the reaction mixture. The use of passive heating elements allows otherwise microwave transparent or poorly absorbing solvents such as hexane, carbon tetrachloride, tetrahydrofuran, dioxane, or toluene to be effectively heated to temperatures far above their boiling points (200-250 degrees C) under sealed vessel microwave conditions. This opens up the possibility to perform microwave synthesis in unpolar solvent environments as demonstrated successfully for several organic transformations, such as Claisen rearrangements, Diels-Alder reactions, Michael additions, N-alkylations, and Dimroth rearrangements. This noninvasive technique is a particularly valuable tool in cases where other options to increase the microwave absorbance of the reaction medium, such as the addition of ionic liquids as heating aids, are not feasible due to an incompatibility of the ionic liquid with a particular substrate. The SiC heating elements are thermally and chemically resistant to 1500 degrees C and compatible with any solvent or reagent.

Confined-Pyrolysis as an Experimental Method for Hydrothermal Organic Synthesis

NASA Technical Reports Server (NTRS)

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

1995-01-01

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

Systems biology approach in plant abiotic stresses.

PubMed

Mohanta, Tapan Kumar; Bashir, Tufail; Hashem, Abeer; Abd Allah, Elsayed Fathi

2017-12-01

Plant abiotic stresses are the major constraint on plant growth and development, causing enormous crop losses across the world. Plants have unique features to defend themselves against these challenging adverse stress conditions. They modulate their phenotypes upon changes in physiological, biochemical, molecular and genetic information, thus making them tolerant against abiotic stresses. It is of paramount importance to determine the stress-tolerant traits of a diverse range of genotypes of plant species and integrate those traits for crop improvement. Stress-tolerant traits can be identified by conducting genome-wide analysis of stress-tolerant genotypes through the highly advanced structural and functional genomics approach. Specifically, whole-genome sequencing, development of molecular markers, genome-wide association studies and comparative analysis of interaction networks between tolerant and susceptible crop varieties grown under stress conditions can greatly facilitate discovery of novel agronomic traits that protect plants against abiotic stresses. Copyright © 2017 Elsevier Masson SAS. All rights reserved.

Abiotic Versus Biotic Weathering Of Olivine As Possible Biosignatures

NASA Technical Reports Server (NTRS)

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

2001-01-01

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.

Biotic and abiotic transformations of methyl tertiary butyl ether (MTBE).

PubMed

Fischer, Axel; Oehm, Claudia; Selle, Michael; Werner, Peter

2005-11-01

Methyl tertiary butyl ether (MTBE) is a fuel additive which is used all over the world. In recent years it has often been found in groundwater, mainly in the USA, but also in Europe. Although MTBE seems to be a minor toxic, it affects the taste and odour of water at concentrations of < 30 microg/L. Although MTBE is often a recalcitrant compound, it is known that many ethers can be degraded by abiotic means. The aim of this study was to examine biotic and abiotic transformations of MTBE with respect to the particular conditions of a contaminated site (former refinery) in Leuna, Germany. Groundwater samples from wells of a contaminated site were used for aerobic and anaerobic degradation experiments. The abiotic degradation experiment (hydrolysis) was conducted employing an ion-exchange resin and MTBE solutions in distilled water. MTBE, tertiary butyl formate (TBF) and tertiary butyl alcohol (TBA) were measured by a gas chromatograph with flame ionisation detector (FID). Aldehydes and organic acids were respectively analysed by a gas chromatograph with electron capture detector (ECD) and high-performance ion chromatography (HPIC). Under aerobic conditions, MTBE was degraded in laboratory experiments. Only 4 of a total of 30 anaerobic experiments exhibited degradation, and the process was very slow. In no cases were metabolites detected, but a few degradation products (TBF, TBA and formic acid) were found on the site, possibly due to the lower temperatures in groundwater. The abiotic degradation of MTBE with an ion-exchange resin as a catalyst at pH 3.5 was much faster than hydrolysis in diluted hydrochloric acid (pH 1.0). Although the aerobic degradation of MTBE in the environment seems to be possible, the specific conditions responsible are widely unknown. Successful aerobic degradation only seems to take place if there is a lack of other utilisable compounds. However, MTBE is often accompanied by other fuel compounds on contaminated sites and anaerobic conditions

Synthesis and Surface-Specific Analysis of Molecular Constituents Relevant to Biogenic Secondary Organic Aerosol Material

NASA Astrophysics Data System (ADS)

Be, A. G.; Upshur, M. A.; Chase, H. M.; Geiger, F.; Thomson, R. J.

2017-12-01

Secondary organic aerosol (SOA) particles formed from the oxidation of biogenic volatile organic compounds (BVOCs) remain a principal, yet elusive, class of airborne particulate matter that impacts the Earth's radiation budget. Given the characteristic molecular complexity comprising biogenic SOA particles, chemical information selective to the gas-aerosol interface may be valuable in the investigation of such systems, as surface considerations likely dictate the phenomena driving particle evolution mechanisms and climate effects. In particular, cloud activation processes may be parameterized using the surface tension depression that coincides with partitioning of surface-active organic species to the gas-droplet interface. However, the extent to which surface chemical processes, such as cloud droplet condensation, are influenced by the chemical structure and reactivity of individual surface-active molecules in SOA particles is largely unknown. We seek to study terpene-derived organic species relevant to the surfaces of biogenic SOA particles via synthesis of putative oxidation products followed by analysis using surface-selective physicochemical measurements. Using dynamic surface tension measurements, considerable differences are observed in the surface tension depression of aqueous pendant droplets that contain synthetically prepared ozonolysis products derived from abundant terpene precursors. Furthermore, sum frequency generation spectroscopy is utilized for comparison of the surface vibrational spectral responses of synthesized reference compounds with those observed for laboratory aerosol toward probing the surface composition of SOA material. Such ongoing findings highlight the underlying importance of molecular structure and reactivity when considering the surface chemistry of biogenic terpene-derived atmospheric aerosols.

Synthesis of Perylene Imide Diones as Platforms for the Development of Pyrazine Based Organic Semiconductors.

PubMed

de Echegaray, Paula; Mancheño, María J; Arrechea-Marcos, Iratxe; Juárez, Rafael; López-Espejo, Guzmán; López Navarrete, J Teodomiro; Ramos, María Mar; Seoane, Carlos; Ortiz, Rocío Ponce; Segura, José L

2016-11-18

There is a great interest in peryleneimide (PI)-containing compounds given their unique combination of good electron accepting ability, high abosorption in the visible region, and outstanding chemical, thermal, and photochemical stabilities. Thus, herein we report the synthesis of perylene imide derivatives endowed with a 1,2-diketone functionality (PIDs) as efficient intermediates to easily access peryleneimide (PI)-containing organic semiconductors with enhanced absorption cross-section for the design of tunable semiconductor organic materials. Three processable organic molecular semiconductors containing thiophene and terthiophene moieties, PITa, PITb, and PITT, have been prepared from the novel PIDs. The tendency of these semiconductors for molecular aggregation have been investigated by NMR spectroscopy and supported by quantum chemical calculations. 2D NMR experiments and theoretical calculations point to an antiparallel π-stacking interaction as the most stable conformation in the aggregates. Investigation of the optical and electrochemical properties of the materials is also reported and analyzed in combination with DFT calculations. Although the derivatives presented here show modest electron mobilities of ∼10 -4 cm 2 V -1 s -1 , these preliminary studies of their performance in organic field effect transistors (OFETs) indicate the potential of these new building blocks as n-type semiconductors.

Soft plasma processing of organic nanowires: a route for the fabrication of 1D organic heterostructures and the template synthesis of inorganic 1D nanostructures.

PubMed

Alcaire, Maria; Sanchez-Valencia, Juan R; Aparicio, Francisco J; Saghi, Zineb; Gonzalez-Gonzalez, Juan C; Barranco, Angel; Zian, Youssef Oulad; Gonzalez-Elipe, Agustin R; Midgley, Paul; Espinos, Juan P; Groening, Pierangelo; Borras, Ana

2011-11-01

Hierarchical (branched) and hybrid metal-NPs/organic supported NWs are fabricated through controlled plasma processing of metalloporphyrin, metallophthalocyanine and perylene nanowires. The procedure is also applied for the development of a general template route for the synthesis of supported metal and metal oxide nanowires.

Indices, multispecies and synthesis descriptors in benthic assessments: Intertidal organic enrichment from oyster farming

NASA Astrophysics Data System (ADS)

Quintino, Victor; Azevedo, Ana; Magalhães, Luísa; Sampaio, Leandro; Freitas, Rosa; Rodrigues, Ana Maria; Elliott, Michael

2012-09-01

Intertidal off-bottom oyster culture is shown to cause organic enrichment of the shore and although there are two stressors of interest (the presence of a structure, the trestles, and also the sediment and organic waste from the oysters), these can be separated and their relative impacts determined using an appropriate nested experimental design and data treatments. Although no artificial food sources are involved, the oysters feeding activity and intensity of culture enhances biodeposition and significantly increases the sediment fines content and total organic matter. This in general impoverished the benthic community in culture areas rather than a species succession with the installation of opportunists or a resulting increase in the abundance and biomass of benthic species; the findings can be a direct consequence of the intertidal situation which is less-amenable recruitment of species more common to the subtidal environment. Thus the most appropriate biological descriptors to diagnose the effects associated with the organic enrichment were the multispecies abundance data as well as the primary biological variables species richness and abundance. The effects were however spatially and statistically significantly confined to the area located directly underneath the culture bags compared to the corridors located between the trestles, which do not show such enrichment effects. Synthesis biotic indices were much less effective to diagnose the benthic alterations associated with this organic enrichment. These results show that special attention must be paid when using indices in areas where the organic enrichment induces an impoverishment of the benthic community but not necessarily a species replacement with the installation of opportunists.

MICOS and phospholipid transfer by Ups2-Mdm35 organize membrane lipid synthesis in mitochondria.

PubMed

Aaltonen, Mari J; Friedman, Jonathan R; Osman, Christof; Salin, Bénédicte; di Rago, Jean-Paul; Nunnari, Jodi; Langer, Thomas; Tatsuta, Takashi

2016-06-06

Mitochondria exert critical functions in cellular lipid metabolism and promote the synthesis of major constituents of cellular membranes, such as phosphatidylethanolamine (PE) and phosphatidylcholine. Here, we demonstrate that the phosphatidylserine decarboxylase Psd1, located in the inner mitochondrial membrane, promotes mitochondrial PE synthesis via two pathways. First, Ups2-Mdm35 complexes (SLMO2-TRIAP1 in humans) serve as phosphatidylserine (PS)-specific lipid transfer proteins in the mitochondrial intermembrane space, allowing formation of PE by Psd1 in the inner membrane. Second, Psd1 decarboxylates PS in the outer membrane in trans, independently of PS transfer by Ups2-Mdm35. This latter pathway requires close apposition between both mitochondrial membranes and the mitochondrial contact site and cristae organizing system (MICOS). In MICOS-deficient cells, limiting PS transfer by Ups2-Mdm35 and reducing mitochondrial PE accumulation preserves mitochondrial respiration and cristae formation. These results link mitochondrial PE metabolism to MICOS, combining functions in protein and lipid homeostasis to preserve mitochondrial structure and function. © 2016 Aaltonen et al.

Synthesis and bioimaging of biodegradable red fluorescent organic nanoparticles with aggregation-induced emission characteristics.

PubMed

Xu, Dazhuang; Zou, Hui; Liu, Meiying; Tian, Jianwen; Huang, Hongye; Wan, Qing; Dai, Yanfeng; Wen, Yuanqing; Zhang, Xiaoyong; Wei, Yen

2017-12-15

Fluorescent organic nanoparticles (FONs) with aggregation-induced emission (AIE) features have recently emerged as promising fluorescent probes for biomedical applications owing to their excellent optical properties, designability and biocompatibility. Significant progress has been made recently for synthesis and biomedical applications of these AIE-active FONs. However, only very limited reports have demonstrated the fabrication of biodegradable AIE-active FONs with red fluorescence emission. In this study, a novel strategy has been developed for the preparation of biodegradable AIE-active polyurethanes (PUs) through a two-step polymerization, in which the diisocyanate-terminated polyethylene glycol (NCO-PEG-NCO) was synthesized and subsequently conjugated with diamine-containing AIE dye (NH 2 -Phe-NH 2 ). The successful synthesis of AIE-active Phe-PEG 2000 PUs is evidenced by a series of characterization techniques. Because of the formation of AIE-active amphiphilic PUs, the final copolymers can self-assemble into spherical nanoparticles, which exhibit strong luminescence and high water dispersion. The biological evaluation results suggest that the AIE-active Phe-PEG 2000 FONs possess low toxicity and desirable cell permeability. Therefore, we anticipate that these AIE-active FONs with biodegradable potential will trigger much research enthusiasm and effort toward the creation of new AIE-active materials with improved properties for various biomedical applications. Copyright © 2017 Elsevier Inc. All rights reserved.

Synthesis of metal-organic framework films by pore diffusion method

NASA Astrophysics Data System (ADS)

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.

Synthesis of NMP, a Fluoxetine (Prozac) Precursor, in the Introductory Organic Laboratory

NASA Astrophysics Data System (ADS)

Perrine, Daniel M.; Sabanayagam, Nathan R.; Reynolds, Kristy J.

1998-10-01

A synthesis of the immediate precursor of the widely used antidepressant fluoxetine (Prozac) is described. The procedure is short, safe, and simple enough to serve as a laboratory exercise for undergraduate students in the second semester of introductory organic chemistry and is one which will be particularly interesting to those planning a career in the health sciences. The compound synthesized is (°)-N,N-dimethyl-3-(p-trifluoromethylphenoxy)-3-phenylpropylamine, or "N-methyl Prozac" (NMP). The synthesis of NMP requires one two-hour period and a second three-hour period. In the first period, a common Mannich base, 3-dimethylaminopropiophenone, is reduced with sodium borohydride to form (°)-3-dimethylamino-1-phenylpropanol. In the second period, potassium t-butoxide is used to couple (°)-3-dimethylamino-1-phenylpropanol with p-chlorotrifluoromethylbenzene to form NMP, which is isolated as its oxalate salt. All processes use equipment and materials that are inexpensive and readily available in most undergraduate laboratories. Detailed physical data are given on NMP, including high-field DEPT 13C NMR.

Synthesis of Organic Matter of Prebiotic Chemistry at the Protoplanetary Disc

NASA Astrophysics Data System (ADS)

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

Abiotic drivers of Chihuahuan Desert plant communities

Treesearch

Laura Marie Ladwig

2014-01-01

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...

Single step synthesis and organization of gold colloids assisted by copolymer templates

NASA Astrophysics Data System (ADS)

Sarrazin, Aurélien; Gontier, Arthur; Plaud, Alexandre; Béal, Jérémie; Yockell-Lelièvre, Hélène; Bijeon, Jean-Louis; Plain, Jérôme; Adam, Pierre-Michel; Maurer, Thomas

2014-06-01

We report here an original single-step process for the synthesis and self-organization of gold colloids by simply incorporating gold salts into a solution prepared using polystyrene (PS)-polymethylmethacrylate copolymer and thiolated PS with propylene glycol methyl ether acetate as a solvent. The spin-coating and annealing of this solution then allows the formation of PS domains. Depending on the polymer concentration of the as-prepared solution, there can be either one or several gold nanoparticles (Au NPs) per PS domain. For high concentrations of Au NPs in PS domains, the coupling between plasmonic NPs leads to the observation of a second peak in the optical extinction spectrum. Such a collective effect could be relevant for the development of optical strain sensors in the near future.

Surface supported gold-organic hybrids: on-surface synthesis and surface directed orientation.

PubMed

Zhang, Haiming; Franke, Jörn-Holger; Zhong, Dingyong; Li, Yan; Timmer, Alexander; Arado, Oscar Díaz; Mönig, Harry; Wang, Hong; Chi, Lifeng; Wang, Zhaohui; Müllen, Klaus; Fuchs, Harald

2014-04-09

The surface-assisted synthesis of gold-organic hybrids on Au (111) and Au (100) surfaces is repotred by thermally initiated dehalogenation of chloro-substituted perylene-3,4,9,10-tetracarboxylic acid bisimides (PBIs). Structures and surface-directed alignment of the Au-PBI chains are investigated by scanning tunnelling microscopy in ultra high vacuum conditions. Using dichloro-PBI as a model system, the mechanism for the formation of Au-PBI dimer is revealed with scanning tunnelling microscopy studies and density functional theory calculations. A PBI radical generated from the homolytic C-Cl bond dissociation can covalently bind a surface gold atom and partially pull it out of the surface to form stable PBI-Au hybrid species, which also gives rise to the surface-directed alignment of the Au-PBI chains on reconstructed Au (100) surfaces. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis and characterization of a novel inorganic-organic hybrid material based on polyoxometalates and dicyclohexylcarbodiimide

NASA Astrophysics Data System (ADS)

Huang, Bo; Hu, Xiaokang; Hu, Xunliang; Wang, Nan; Yang, Kang; Xiao, Zicheng; Wu, Pingfan

2017-12-01

Towards design and synthesis of bulky molecules and molecular machines, we reported a new inorganic-organic hybrid material based on polyoxometalates and 1, 3-dicyclohexylcarbodiimide (DCC): (Bu4N)2[V6O13{(OCH2)3CCH2OOCCH2CH2CON(C6H11)CONHC6H11}2]. The hybrid was characterized by FT-IR, 1H NMR, UV-Vis, ESI-MS, and the structure of the compound was determined through single-crystal X-ray diffraction. There was an interesting supramolecular assembly in the hybrid material through intermolecular hydrogen bonding, and each cyclohexyl in the polymer looks like one of blades in the propeller. Furthermore, the thermal stability of the hybrid was tested by TGA analyses, and the electrochemical property has also been studied by cyclic voltammogram.

Materials for n-type organic electronics: synthesis and properties of fluoroarene-thiophene semiconductors

NASA Astrophysics Data System (ADS)

Facchetti, Antonio; Yoon, Myung-Han; Katz, Howard E.; Marks, Tobin J.

2003-11-01

Recent progress in the field of organic electronics is due to a fruitful combination of both innovative molecular design and promising low-cost material/device assembly. Targeting the first strategy, we present here the general synthesis of fluoroarene-containing thiophene-based semiconductors and the study of their properties with respect to the corresponding fluorine-free hole-transporting analogues. The new compounds have been characterized by elemental analysis, mass spectrometry, and 1H- and 19F NMR. The dramatic influence of fluorine substitution and molecular architecture has been investigated by solution/film optical absorption, fluorescence emission, and cyclic voltammetry. Single crystal data for all of the oligomers have been obtained and will be presented. Film microstructure and morphology of this new class of materials have been studied by XRD and SEM. Particular emphasis will be posed on the solution-processable oligomers and polymers.

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

PubMed Central

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

2011-01-01

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

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

NASA Astrophysics Data System (ADS)

Luridiana, Alberto; Pretta, Gianluca; Secci, Francesco; Frongia, Angelo; Chiriu, Daniele; Carbonaro, Carlo Maria; Corpino, Riccardo; Ricci, Pier Carlo

2014-10-01

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.

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

SciTech Connect

Luridiana, Alberto; Pretta, Gianluca; Secci, Francesco

2014-10-21

It is well known that stilbene with a trans conformation is highly fluorescent. From the viewpoint of molecular structure, coumarins bear a carbon-carbon double bond which is fixed as trans conformation as in trans-stilbene through a lactone structure. This can help to avoid the trans-cis transformation of the double bond under ultraviolet (UV) irradiation as observed in stilbene compounds and results in strong fluorescence and high fluorescence quantum yield and photostability in most of coumarin derivatives. Herein we report some preliminary results about the synthesis and spectroscopic characterization of tunable coumarins and the development of a new linkage protocol formore » 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.« less

Synthesis, functionalization, and applications of metal-organic frameworks in biomedicine.

PubMed

Chen, Wei; Wu, Chunsheng

2018-02-13

Metal-organic frameworks (MOFs), also known as coordination polymers, have attracted extensive research interest in the past few decades due to their unique physical structures and potentially vast applications. In this review, we outline the recent progress in the synthesis, functionalization and applications of MOFs in biomedicine, mainly focusing on two promising, yet challenging areas, i.e., drug delivery and biosensing applications. A major challenge is the proper functionalization of MOFs with demanding properties suitable for biomedical applications. Extensive studies on MOFs in biomedicine have led to substantial progress in the control of key properties of MOFs such as toxicity, size and shape, and biological stability. Due to their flexible composition, pore size and easy functionalization properties, MOFs can be utilized as key components for the development of various functional systems, and their applications in drug delivery and biosensing are reviewed. Future trends and perspectives in these research areas are also outlined.

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

PubMed

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

2014-06-24

This unit describes a highly effective method to produce 5'-O-DMT-2'-O-TBS mononucleosides selectively using a small organic catalyst. This methodology avoids the tedious protection/deprotection strategy necessary to differentiate the 2'- and 3'-hydroxyl groups in a ribonucleoside. The catalyst was synthesized in two steps, starting from the condensation of valinol and cyclopentyl aldehyde, followed by anionic addition of N-methylimidazole. Ring closure of the amino alcohol with N,N-dimethylformamide dimethyl acetal in methanol furnishes the catalyst. All four 2'-O-TBS protected mono-nucleosides, U, A(Bz), G(Ib), and C(Ac), were produced in a single step using 10 to 20 mol% of the catalyst at room temperature with excellent yields and selectivity. Further transformation to phosphoramidite demonstrates the utility of this protocol in the preparation of monomers useful for automated synthesis of RNA. Copyright © 2014 John Wiley & Sons, Inc.

Effects of pH and Redox Gradients on Prebiotic Organic Synthesis and the Generation of Free Energy in Simulated Hydrothermal Systems

NASA Astrophysics Data System (ADS)

Barge, L. M.; Flores, E.; Abedian, Y.; Maltais, T.; Cameron, R.; Hermis, N.; Chin, K.; Russell, M. J.; Baum, M. M.

2017-07-01

Hydrothermal minerals in alkaline vents can promote phosphorus and organic concentration, redox reactions driven by catalytic metal sulfides, and the ambient pH and redox gradients can affect the synthesis of organics.

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

ERIC Educational Resources Information Center

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

2016-01-01

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

Graphic organizers and their effects on the reading comprehension of students with LD: a synthesis of research.

PubMed

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

2004-01-01

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.

General Chemistry Laboratory Experiment to Demonstrate Organic Synthesis, Fluorescence, and Chemiluminescence through Production of a Biphasic Glow Stick

ERIC Educational Resources Information Center

Pay, Adam L.; Kovash, Curtiss; Logue, Brian A.

2017-01-01

A laboratory experiment is described for beginning, nonmajor chemistry students, which allows students to examine the phenomena of fluorescence and chemiluminescence, as well as gain experience in basic organic synthesis. Students synthesize fluorescein and bis(2,4,6-trichlorophenyl) oxalate (TCPO) to explore fluorescence and chemiluminescence by…

Facile room-temperature solution-phase synthesis of a spherical covalent organic framework for high-resolution chromatographic separation.

PubMed

Yang, Cheng-Xiong; Liu, Chang; Cao, Yi-Meng; Yan, Xiu-Ping

2015-08-07

A simple and facile room-temperature solution-phase synthesis was developed to fabricate a spherical covalent organic framework with large surface area, good solvent stability and high thermostability for high-resolution chromatographic separation of diverse important industrial analytes including alkanes, cyclohexane and benzene, α-pinene and β-pinene, and alcohols with high column efficiency and good precision.

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

ERIC Educational Resources Information Center

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

1985-01-01

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

A one pot organic/CdSe nanoparticle hybrid material synthesis with in situ π-conjugated ligand functionalization.

PubMed

Mazzio, Katherine A; Okamoto, Ken; Li, Zhi; Gutmann, Sebastian; Strein, Elisabeth; Ginger, David S; Schlaf, Rudy; Luscombe, Christine K

2013-02-14

A one pot method for organic/colloidal CdSe nanoparticle hybrid material synthesis is presented. Relative to traditional ligand exchange processes, these materials require smaller amounts of the desired capping ligand, shorter syntheses and fewer processing steps, while maintaining nanoparticle morphology.

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

PubMed

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

2015-08-14

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.

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

ERIC Educational Resources Information Center

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

2012-01-01

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

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

ERIC Educational Resources Information Center

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

2010-01-01

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

The shock synthesis of complex organics from impacts into cometary analogue mixtures

NASA Astrophysics Data System (ADS)

Price, M.; Wozniakiewicz, P.; Cole, M.; Martins, Z.; Burchell, M.

2014-07-01

Introduction: If amino acids are required for the evolution of life, what was their source? Many different theories abound as to the source of amino acids on the early Earth including exogenous delivery from comets/asteroids (for example, glycine was found recently on comet Wild-2 [1]), formation in the protoplanetary nebula [2], or UV catalysed reactions of gases [3]. An alternative explanation is that amino acids can be shock-synthesised during the impact on an icy body onto a rocky body (or, equivalently, the impact of rocky body onto an icy surface). This theory is supported by computer simulations [4] and by very recent experimental data, which demonstrated the formation of simple (including abiotic) amino acids from shocks into ice mixtures mimicking the composition of comets and the surfaces of the icy Jovian and Saturnian satellites. Although the results from these experiments are fundamentally important, the yield of synthesised amino acids was low (nano-grams of material), complicating their detection and identification. In order to increase the collected yield of complex organics, and aid in their detection and identification, we have implemented a new collection technique within our hypervelocity impact facility. Experimental Methodology: Figure 1A) shows a low-resolution high-speed photograph of an impact plasma generated from an impact of a stainless-steel sphere into a mixture of water, CO_{2}, ammonia, and methanol ices. The plasma has an intense blue colour, and lasted for < 1 msec (the frame-rate of the camera). It is during and within this flash that complex organics are most likely synthesised, and thus to maximise the collection of these materials, we have implemented a new collection mechanism. Figure 1B) shows the prototype collection mechanism. Here an aluminium cold-plate (˜150 K) is placed in front of the target holder containing the ice mixtures. The plate has a central hole which allows the projectile to pass through to impact the ice

Assessment of derelict soil quality: Abiotic, biotic and functional approaches.

PubMed

Vincent, Quentin; Auclerc, Apolline; Beguiristain, Thierry; Leyval, Corinne

2018-02-01

The intensification and subsequent closing down of industrial activities during the last century has left behind large surfaces of derelict lands. Derelict soils have low fertility, can be contaminated, and many of them remain unused. However, with the increasing demand of soil surfaces, they might be considered as a resource, for example for non-food biomass production. The study of their physico-chemical properties and of their biodiversity and biological activity may provide indications for their potential re-use. The objective of our study was to investigate the quality of six derelict soils, considering abiotic, biotic, and functional parameters. We studied (i) the soil bacteria, fungi, meso- and macro-fauna and plant communities of six different derelict soils (two from coking plants, one from a settling pond, two constructed ones made from different substrates and remediated soil, and an inert waste storage one), and (ii) their decomposition function based on the decomposer trophic network, enzyme activities, mineralization activity, and organic pollutant degradation. Biodiversity levels in these soils were high, but all biotic parameters, except the mycorrhizal colonization level, discriminated them. Multivariate analysis showed that biotic parameters co-varied more with fertility proxies than with soil contamination parameters. Similarly, functional parameters significantly co-varied with abiotic parameters. Among functional parameters, macro-decomposer proportion, enzyme activity, average mineralization capacity, and microbial polycyclic aromatic hydrocarbon degraders were useful to discriminate the soils. We assessed their quality by combining abiotic, biotic, and functional parameters: the compost-amended constructed soil displayed the highest quality, while the settling pond soil and the contaminated constructed soil displayed the lowest. Although differences among the soils were highlighted, this study shows that derelict soils may provide a

Elucidating the Role of Carbon Sources on Abiotic and Biotic Release of Arsenic into Cambodian Aquifers

NASA Astrophysics Data System (ADS)

Koeneke, M.

2017-12-01

Arsenic (As) is a naturally occurring contaminant in Cambodia that has been contaminating well-water sources of millions of people. Commonly, studies look into the biotic factors that cause the arsenic to be released from aquifer sediments to groundwater. However, abiotic release of As from sediments, though little studied, may also play key roles in As contamination of well water. The goal of this research is to quantitatively compare organic-carbon mediated abiotic and biotic release of arsenic from sediments to groundwater. Batch anaerobic incubation experiments under abiotic (sodium azide used to immobilize microbes) and biotic conditions were conducted using Cambodian aquifer sediments, four different organic carbon sources (sodium lactate, sodium citrate, sodium oxalate, and humic acid), and six different carbon concentrations (0, 1, 2.5, 5, 10, 25mg C/L). Dissolved arsenic, iron(Fe), and manganese(Mn) concentrations in the treatments were measured 112 days . In addition, sediment and solution carbon solution was measured . Collectively, these show how different carbon sources, different carbon concentrations, and how abiotic and biotic factors impact the release of arsenic from Cambodian sediments into aquifers. Overall, an introduction of organic carbon to the soil increases the amount of As released from the sediment. The biotic + abiotic and abiotic conditions seemed to play a minimal role in the amount of As released. Dissolved species analysis showed us that 100% of the As was As(V), Our ICP-MS results vary due to the heterogeneity of samples, but when high levels are Fe are seen in solution, we also see high levels of As. We also see higher As concentrations when there is a smaller amount of Mn in solution.

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

PubMed Central

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

2012-01-01

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

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

NASA Technical Reports Server (NTRS)

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

2002-01-01

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

Enhanced Enzymatic Synthesis of a Cephalosporin, Cefadroclor, in the Presence of Organic Co-solvents.

PubMed

Liu, Kun; Li, Sha; Pang, Xiao; Xu, Zheng; Li, Dengchao; Xu, Hong

2017-05-01

In this study, we investigated the enzymatic synthesis of a semi-synthetic cephalosporin, cefadroclor, from 7-aminodesacetoxymethyl-3-chlorocephalosporanic acid (7-ACCA) and p-OH-phenylglycine methyl ester (D-HPGM) using immobilized penicillin G acylase (IPA) in organic co-solvents. Ethylene glycol (EG) was employed as a component of the reaction mixture to improve the yield of cefadroclor. EG was found to increase the yield of cefadroclor by 15-45%. An investigation of altered reaction parameters including type and concentration of organic solvents, pH of reaction media, reaction temperature, molar ratio of substrates, enzyme loading, and IPA recycling was carried out in the buffer mixture. The best result was a 76.5% conversion of 7-ACCA, which was obtained from the reaction containing 20% EG (v/v), D-HPGM to 7-ACCA molar ratio of 4:1 and pH 6.2, catalyzed by 16 IU mL -1 IPA at 20 °C for 10 h. Under the optimum conditions, no significant loss of IPA activity was found after seven repeated reaction cycles. In addition, cefadroclor exhibited strong inhibitory activity against yeast, Bacillus subtilis NX-2, and Escherichia coli and weaker activity against Staphylococcus aureus and Pseudomonas aeruginosa. Cefadroclor is a potential antibiotic with activity against common pathogenic microorganisms.

Synthesis of Frontalin, the Aggregation Pheromone of the Southern Pine Beetle: A Multistep Organic Synthesis for Undergraduate Students.

ERIC Educational Resources Information Center

Bartlett, Paul A.; And Others

1984-01-01

Background information and experimental procedures are provided for the multistep synthesis of frontalin. The experiment exposes students to a range of practical laboratory problems and important synthetic reactions and provides experiences in working on a medium-size, as well as a relatively small-size scale. (JN)

An Abiotic Glass-Bead Collector Exhibiting Active Transport

NASA Astrophysics Data System (ADS)

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

2015-09-01

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

DEMONSTRATION BULLETIN: METAL-ENHANCED ABIOTIC DEGRADATION TECHNOLOGY - ENVIROMETAL TECHNOLOGIES, INC.

EPA Science Inventory

EnviroMetal Technologies, Inc. (ETI), of Guelph, ON, Canada, has developed the metal-enhanced abiotic degradation technology to treat halogenated volatile organic compounds (VOC) in water. A reactive, zero-valent, granular iron medium causes reductive dehalogenation of VOCs yield...

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

USDA-ARS?s Scientific Manuscript database

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

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

SciTech Connect

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

2016-03-15

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

Role of sugars under abiotic stress.

PubMed

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

2016-12-01

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.

Cortex proliferation in the root is a protective mechanism against abiotic stress.

PubMed

Cui, Hongchang

2015-01-01

Although as an organ the root plays a pivotal role in nutrient and water uptake as well anchorage, individual cell types function distinctly. Cortex is regarded as the least differentiated cell type in the root, but little is known about its role in plant growth and physiology. In recent studies, we found that cortex proliferation can be induced by oxidative stress. Since all types of abiotic stress lead to oxidative stress, this finding suggests a role for cortex in coping with abiotic stress. This hypothesis was tested in this study using the spy mutant, which has an extra layer of cortex in the root. Interestingly, the spy mutant was shown to be hypersensitive to salt and oxidizing reagent applied to the leaves, but it was as tolerant as the wild type to these compounds in the soil. This result lends support to the notion that cortex has a protective role against abiotic stress arising from the soil.

Synthesis and Characterization of Transition Metal Oxides and Dichalcogenides and Their Application in Organic Photovoltaics

NASA Astrophysics Data System (ADS)

Mendez, Diego Barrera

This Ph.D. research focused on the development of new materials for alternative renewable energy using organic photovoltaics (OPVs). The first step was to established reliable fabrication and characterization methods of organic photovoltaic devices. The reproducibility of organic photovoltaic cell performance is one of the essential issues that must be achieved before engaging serious investigations of the applications of creative and challenging ideas. Secondly, we thoroughly studied the surface chemistry of the underlying layer and its critical role on the morphology of the BHJ active layer. We showed that when the active layer (which consists of blends of poly(3-hexylthiophene) (P3HT) and phenyl-C60-butyric acid methyl ester (PCBM)) is deposited and annealed over a sol-gel ZnO electron transport layer surface made from monoethanolamine (MEA) containing precursor, PCBM clusters form during annealing and this phase segregation leads to a drastic reduction of OPV parameters due to both low charge generation and high bimolecular recombination. Rinsing the pyrolyzed ZnO films with solvents or using a ZnO recipe without MEA significantly reduced the formation of PCBM clusters and produced devices with good performance. Third, we developed new materials suitable for low-temperature processing and large-area deposition methods to be used as transport layer on OPVs. We achieved the synthesis of MoOx suspensions suitable for large area deposition, with controlled size, stoichiometry, and electronic properties using controlled oxidative dissolution of organometallic powders with H2O2 in n-butanol. The small nanoparticle diameters of ˜ 2 nm enabled solution processing of nanoparticle films on ITO with electronic properties comparable to solution processed and vacuum deposited counterparts, without the need for any post processing. We also accomplished the synthesis of transition metal dichalcogenides (TMDs) directly from precursors in solution using a versatile synthesis

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

NASA Astrophysics Data System (ADS)

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

2016-03-01

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

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

NASA Astrophysics Data System (ADS)

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

2017-05-01

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.

Abiotic Formation of Methyl Halides in the Terrestrial Environment

NASA Astrophysics Data System (ADS)

Keppler, F.

2011-12-01

Methyl chloride and methyl bromide are the most abundant chlorine and bromine containing organic compounds in the atmosphere. Since both compounds have relatively long tropospheric lifetimes they can effectively transport halogen atoms from the Earth's surface, where they are released, to the stratosphere and following photolytic oxidation form reactive halogen gases that lead to the chemical destruction of ozone. Methyl chloride and methyl bromide account for more than 20% of the ozone-depleting halogens delivered to the stratosphere and are predicted to grow in importance as the chlorine contribution to the stratosphere from anthropogenic CFCs decline. Today methyl chloride and methyl bromide originate mainly from natural sources with only a minor fraction considered to be of anthropogenic origin. However, until as recently as 2000 most of the methyl chloride and methyl bromide input to the atmosphere was considered to originate from the oceans, but investigations in recent years have clearly demonstrated that terrestrial sources such as biomass burning, wood-rotting fungi, coastal salt marshes, tropical vegetation and organic matter degradation must dominate the atmospheric budgets of these trace gases. However, many uncertainties still exist regarding strengths of both sources and sinks, as well as the mechanisms of formation of these naturally occurring halogenated gases. A better understanding of the atmospheric budget of both methyl chloride and methyl bromide is therefore required for reliable prediction of future ozone depletion. Biotic and abiotic methylation processes of chloride and bromide ion are considered to be the dominant pathways of formation of these methyl halides in nature. In this presentation I will focus on abiotic formation processes in the terrestrial environment and the potential parameters that control their emissions. Recent advances in our understanding of the abiotic formation pathway of methyl halides will be discussed. This will

On-Surface Synthesis and Reactivity of Functional Organic and Metal-Organic Adsorbates at Metal Surfaces by Vibrational Spectroscopy

NASA Astrophysics Data System (ADS)

Williams, Christopher Glen

Surface self-assembly is a promising way to introduce functionality to a surface through design at the molecular level. These self-assembled species allow for new on-surface type reactions to be observed and studied. The experiments described in this thesis demonstrate that the molecules used in self-assembly can potentially lead to interesting synthesis pathways and can be used to explore previously under-researched reaction pathways and surface molecular architecture activity or stability. Alkanes are an unreactive species typically used for driving molecular assembly in surface structures. However, with molecular design, alkanes are capable of reacting on surfaces not typically associated with alkane reactivity. Utilizing high-resolution electron energy loss spectroscopy (HREELS) and octaethylporphyrin, we could observe that dehydrogenation is possible on Cu(100) and Ag(111) surfaces at 500 and 610 K respectively. HREELS revealed that after the dehydrogenation, the molecule undergoes an intramolecular C-C bond formation leading to a tetrabenzo-porphyrin structure. Controls with deposited tetrabenzo-porphyrin were performed to verify the structure. This work provides the first example of dehydrocyclization on Cu(100) and Ag(111) to be analyzed by vibrational spectroscopy. Alkyl species in the 1,3,5-tris-(3,5-diethylphenyl)benzene molecule also undergo a dehydrogenation on Cu(100) and Au(111) at 450 and 500 K. The design of this molecule does not let the intramolecular dehydrocyclization reaction take place, but instead the dehydrogenation leads to intermolecular C-C bond formation between molecular species as noted by the formation of extended structure across the surface. Controls with triphenyl-benzene were done to help characterize the peaks in the spectra and observe varying reactivity when the ethyl groups are absent. The fabrication of uniform single-site metal centers at surfaces is important for higher selectivity in next-generation heterogeneous

Synthesis and fluorescent properties of poly(arylpyrazoline)'s for organic-electronics

NASA Astrophysics Data System (ADS)

Vandana, T.; Ramkumar, V.; Kannan, P.

2016-08-01

The present work focuses on the synthesis and characterization of poly(arylchalcone)'s (PCH I-IV) by reacting acetone with various dialdehydes for the first time at below ambient temperature followed by cyclization with phenylhydrazinehydrochloride to yield luminescent poly(arylpyrazoline)'s (PPY I-IV). The synthesized polymers were characterized by standard techniques such as, GPC, SEM, TGA, FT-IR, 1H NMR, UV-Vis absorption and fluorescence spectroscopy, and electrochemical studies by cyclic voltammetry analyses. The Pyrazoline group hooked with different aryl donors such as benzene, thiophene, carbazole, triphenylamine, thus results a series of blue and green emitting materials. The obtained optical bandgap energy of the polymers (PPY I-IV) were 2.53, 3.41, 3.07, 3.10 eV respectively, suggest that all the polymers belongs to semiconducting category. The solvent effect of polymers was thoroughly studied and explained by Lippert-Mataga equation. The polymers I & IV display large degree of intra-molecular charge transfer in excited state evidenced from solvatochromic shift on the emission spectra. The obtained results demonstrate that they are promising materials for organic electronics applications.

Synthesis, structural, optical and thermal studies of an organic nonlinear optical 4-aminopyridinium maleate single crystal.

PubMed

Pandi, P; Peramaiyan, G; Kumar, M Krishna; Kumar, R Mohan; Jayavel, R

2012-03-01

Synthesis and growth of a novel organic nonlinear optical (NLO) crystal of 4-aminopyridinium maleate (4APM) in larger size by the slow evaporation solution growth technique are reported. Single crystal and powder X-ray diffraction analyses reveal that 4APM crystallizes in monoclinic system with space group P2(1) with cell parameters a=8.140(4)Å, b=5.457(5)Å, c=10.926(10)Å and volume=481.4(7)Å(3). The grown crystal has been characterized by Fourier transform infrared and UV-visible spectral analyses. Thermogravimetric analysis (TGA) and differential thermal analysis (DTA) have been carried out to study its thermal properties. Dielectric measurements have been carried out to study the distribution of charges within the crystal. The mechanical strength of the crystal has been studied by using Vickers' microhardness test. The etching studies have been carried out on the grown crystal. The Kurtz and Perry powder SHG technique confirms the NLO property of the grown crystal and the SHG efficiency of 4APM was found to be 4.8 times greater than that of KDP crystal. Copyright © 2011 Elsevier B.V. All rights reserved.

Electrochemical synthesis of self-organized TiO2 crystalline nanotubes without annealing

NASA Astrophysics Data System (ADS)

Giorgi, Leonardo; Dikonimos, Theodoros; Giorgi, Rossella; Buonocore, Francesco; Faggio, Giuliana; Messina, Giacomo; Lisi, Nicola

2018-03-01

This work demonstrates that upon anodic polarization in an aqueous fluoride-containing electrolyte, TiO2 nanotube array films can be formed with a well-defined crystalline phase, rather than an amorphous one. The crystalline phase was obtained avoiding any high temperature annealing. We studied the formation of nanotubes in an HF/H2O medium and the development of crystalline grains on the nanotube wall, and we found a facile way to achieve crystalline TiO2 nanotube arrays through a one-step anodization. The crystallinity of the film was influenced by the synthesis parameters, and the optimization of the electrolyte composition and anodization conditions (applied voltage and time) were carried out. For comparison purposes, crystalline anatase TiO2 nanotubes were also prepared by thermal treatment of amorphous nanotubes grown in an organic bath (ethylene glycol/NH4F/H2O). The morphology and the crystallinity of the nanotubes were studied by field emission gun-scanning electron microscopy (FEG-SEM) and Raman spectroscopy, whereas the electrochemical and semiconducting properties were analyzed by means of linear sweep voltammetry, impedance spectroscopy, and Mott-Schottky plots. X-ray photoelectron spectroscopy (XPS) and ultraviolet photoelectron spectroscopy (UPS) allowed us to determine the surface composition and the electronic structure of the samples and to correlate them with the electrochemical data. The optimal conditions to achieve a crystalline phase with high donor concentration are defined.

Metal-Organic Polyhedral Core as a Versatile Scaffold for Divergent and Convergent Star Polymer Synthesis.

PubMed

Hosono, Nobuhiko; Gochomori, Mika; Matsuda, Ryotaro; Sato, Hiroshi; Kitagawa, Susumu

2016-05-25

We herein report the divergent and convergent synthesis of coordination star polymers (CSP) by using metal-organic polyhedrons (MOPs) as a multifunctional core. For the divergent route, copper-based great rhombicuboctahedral MOPs decorated with dithiobenzoate or trithioester chain transfer groups at the periphery were designed. Subsequent reversible addition-fragmentation chain transfer (RAFT) polymerization of monomers mediated by the MOPs gave star polymers, in which 24 polymeric arms were grafted from the MOP core. On the other hand, the convergent route provided identical CSP architectures by simple mixing of a macroligand and copper ions. Isophthalic acid-terminated polymers (so-called macroligands) immediately formed the corresponding CSPs through a coordination reaction with copper(II) ions. This convergent route enabled us to obtain miktoarm CSPs with tunable chain compositions through ligand mixing alone. This powerful method allows instant access to a wide variety of multicomponent star polymers that conventionally have required highly skilled and multistep syntheses. MOP-core CSPs are a new class of star polymer that can offer a design strategy for highly processable porous soft materials by using coordination nanocages as a building component.

The atmosphere of the primitive earth and the prebiotic synthesis of organic compounds

NASA Technical Reports Server (NTRS)

Miller, S. L.; Schlesinger, G.

1983-01-01

The prebiotic synthesis of organic compounds is investigated using a spark discharge on various simulated prebiotic atmospheres at 25 C. It is found that glycine is almost the only amino acid produced from the model atmospheres containing CO and CO2. These results show that the maximum yield is about the same for the three carbon sources (CO, CO2, and CH4) at high H2/carbon ratios, but that CH4 is superior at low H2/carbon ratios. CH4 is found to yield a much greater variety of amino acids than either CO or CO2. If it is assumed that amino acids more complex than glycine were required for the origin of life, then these findings indicate the need for CH4 in the primitive atmosphere. The yields of cyanide and formaldehyde are shown to parallel the amino acid results, with yields of HCN and H2CO as high as 13 percent based on carbon. Ammonia is also found to be produced from N2 in experiments with no added NH3 in yields as high as 4.9 percent. These results indicate that large amounts of NH3 would have been synthesized on the primitive earth by electric discharges.

Synthesis, characterization, and applications of electroactive polymeric nanostructures for organic coatings

NASA Astrophysics Data System (ADS)

Suryawanshi, Abhijit Jagnnath

Electroactive polymers (EAP) such as polypyrrole (PPy) and polyaniline (PANI) are being explored intensively in the scientific community. Nanostructures of EAPs have low dimensions and high surface area enabling them to be considered for various useful applications. These applications are in several fields including corrosion inhibition, capacitors, artificial muscles, solar cells, polymer light emitting diodes, and energy storage devices. Nanostructures of EAPs have been synthesized in different morphologies such as nanowires, nanorods, nanotubes, nanospheres, and nanocapsules. This variety in morphology is traditionally achieved using soft templates, such as surfactant micelles, or hard templates, such as anodized aluminum oxide (AAO). Templates provide stability and groundwork from which the polymer can grow, but the templates add undesirable expense to the process and can change the properties of the nanoparticles by integrating its own properties. In this study a template free method is introduced to synthesize EAP nanostructures of PPy and PANI utilizing ozone oxidation. The simple techniques involve ozone exposure to the monomer solution to produce aqueous dispersions of EAP nanostructures. The synthesized nanostructures exhibit uniform morphology, low particle size distribution, and stability against agglomeration. Ozone oxidation is further explored for the synthesis of silver-PPy (Ag-PPy) core-shell nanospheres (CSNs). Coatings containing PPy nanospheres were formulated to study the corrosion inhibition efficiency of PPy nanospheres. Investigation of the coatings using electrochemical techniques revealed that the PPy nanospheres may provide corrosion inhibition against filiform corrosion by oxygen scavenging mechanism. Finally, organic corrosion inhibitors were incorporated in PPy to develop efficient corrosion inhibiting systems, by using the synergistic effects from PPy and organic corrosion inhibitors.

Synthesis of Very-Long-Chain Fatty Acids in the Epidermis Controls Plant Organ Growth by Restricting Cell Proliferation

PubMed Central

Nobusawa, Takashi; Okushima, Yoko; Nagata, Noriko; Kojima, Mikiko; Sakakibara, Hitoshi; Umeda, Masaaki

2013-01-01

Plant organ growth is controlled by inter-cell-layer communication, which thus determines the overall size of the organism. The epidermal layer interfaces with the environment and participates in both driving and restricting growth via inter-cell-layer communication. However, it remains unknown whether the epidermis can send signals to internal tissue to limit cell proliferation in determinate growth. Very-long-chain fatty acids (VLCFAs) are synthesized in the epidermis and used in the formation of cuticular wax. Here we found that VLCFA synthesis in the epidermis is essential for proper development of Arabidopsis thaliana. Wild-type plants treated with a VLCFA synthesis inhibitor and pasticcino mutants with defects in VLCFA synthesis exhibited overproliferation of cells in the vasculature or in the rib zone of shoot apices. The decrease of VLCFA content increased the expression of IPT3, a key determinant of cytokinin biosynthesis in the vasculature, and, indeed, elevated cytokinin levels. These phenotypes were suppressed in ipt3;5;7 triple mutants, and also by vasculature-specific expression of cytokinin oxidase, which degrades active forms of cytokinin. Our results imply that VLCFA synthesis in the epidermis is required to suppress cytokinin biosynthesis in the vasculature, thus fine-tuning cell division activity in internal tissue, and therefore that shoot growth is controlled by the interaction between the surface (epidermis) and the axis (vasculature) of the plant body. PMID:23585732

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

PubMed

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

2014-01-01

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.

Challenges in systematic reviews: synthesis of topics related to the delivery, organization, and financing of health care.

PubMed

Bravata, Dena M; McDonald, Kathryn M; Shojania, Kaveh G; Sundaram, Vandana; Owens, Douglas K

2005-06-21

Some important health policy topics, such as those related to the delivery, organization, and financing of health care, present substantial challenges to established methods for evidence synthesis. For example, such reviews may ask: What is the effect of for-profit versus not-for-profit delivery of care on patient outcomes? Or, which strategies are the most effective for promoting preventive care? This paper describes innovative methods for synthesizing evidence related to the delivery, organization, and financing of health care. We found 13 systematic reviews on these topics that described novel methodologic approaches. Several of these syntheses used 3 approaches: conceptual frameworks to inform problem formulation, systematic searches that included nontraditional literature sources, and hybrid synthesis methods that included simulations to address key gaps in the literature. As the primary literature on these topics expands, so will opportunities to develop additional novel methods for performing high-quality comprehensive syntheses.

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

PubMed

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

2015-02-07

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

A Safer and Convenient Synthesis of Sulfathiazole for Undergraduate Organic and Medicinal Chemistry Classes

ERIC Educational Resources Information Center

Boyle, Jeff; Otty, Sandra; Sarojini, Vijayalekshmi

2012-01-01

A safer method for the synthesis of the sulfonamide drug sulfathiazole, for undergraduate classes, is described. This method improves upon procedures currently followed in several undergraduate teaching laboratories for the synthesis of sulfathiazole. Key features of this procedure include the total exclusion of pyridine, which has potential…

Green Synthesis of Organics and Nanomaterials and Sustainable Applications of Nano-Catalysts- HESTEC

EPA Science Inventory

The presentation summarizes our green chemical synthesis activity 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 o...

Green Synthesis of Organics and Nanomaterials and Sustainable Applications of Nano-Catalysts

EPA Science Inventory

The presentation summarizes our green chemical synthesis activity 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 o...

Microwave-Assisted Eco-Friendly Synthesis of Organics and Nanomaterials

EPA Science Inventory

This presentation summarizes our recent activity in MW-assisted synthesis, which involves benign alternatives, such as the use of supported reagents, and greener reaction medium in aqueous or solvent-free conditions.1 The greener synthesis of heterocyclic compounds, coupling reac...

Eco-friendly Synthesis of Organics and Nanomaterials: Sustainable Applications of Nano-Catalysts

EPA Science Inventory

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 varie...

Greener Synthesis of Organics and Nanomaterials: Sustainable Applications of Nano-Catalysts

EPA Science Inventory

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 varie...

Synthesis of 5,5-Diphenyl-4-penten-2-One: A Variation on a Classic Organic Synthesis Laboratory

ERIC Educational Resources Information Center

Alber, Joshua P.; DeGrand, Michael J.; Cermak, Diana M.

2011-01-01

The Grignard reaction and the addition of protecting groups are standard reactions in an organic chemistry course. Organic students learn about the "quench" step of the Grignard reaction using acid and water and the acid-catalyzed hydrolysis to remove the protecting group, yet in the lecture students find these two reactions to be confusing in…

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

ERIC Educational Resources Information Center

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

2015-01-01

This advanced undergraduate laboratory experiment involves the synthesis and characterization of a metal-organic framework with microporous channels that are held intact via hydrogen bonding of the coordinated water molecules. The hydrothermal synthesis of Co[subscript 3](BTC)[subscript 2]·12H[subscript 2]O (BTC = 1,3,5-benzene tricarboxylic acid)…

Hierarchical Metal–Organic Framework Hybrids: Perturbation-Assisted Nanofusion Synthesis

DOE PAGES

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

2015-12-04

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 hierarchicalmore » 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. Our 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

Low melatonin production by suppression of either serotonin N-acetyltransferase or N-acetylserotonin methyltransferase in rice causes seedling growth retardation with yield penalty, abiotic stress susceptibility, and enhanced coleoptile growth under anoxic conditions.

PubMed

Byeon, Yeong; Back, Kyoungwhan

2016-04-01

Serotonin N-acetyltransferase (SNAT) and N-acetylserotonin methyltransferase (ASMT) are the last two key enzymes for melatonin biosynthesis in living organisms. In this study, we demonstrated that transgenic rice (Oryza sativa L.) plants, in which expression of either endogenous SNAT or ASMT was suppressed, had reduced melatonin synthesis, confirming that both SNAT and ASMT are functionally involved in melatonin synthesis. The melatonin-deficient SNAT rice had retarded seedling growth, which was partially restored by exogenous melatonin application, suggesting melatonin's role in seedling growth. In addition, the plants were more sensitive to various abiotic stresses, including salt and cold, compared with the wild type. Melatonin-deficient SNAT rice had increased coleoptile growth under anoxic conditions, indicating that melatonin also inversely regulates plant growth under anaerobic conditions with the concomitant high expression of alcohol dehydrogenase genes. Similarly, the melatonin-deficient ASMT rice exhibited accelerated senescence in detached flag leaves, as well as significantly reduced yield. These loss-of-function studies on the melatonin biosynthetic genes confirmed most previous pharmacological reports that melatonin not only promotes plant growth but also mitigates various abiotic stresses. © 2016 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

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

PubMed

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

2017-09-21

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.

Abscisic Acid and abiotic stress signaling.

PubMed

Tuteja, Narendra

2007-05-01

Abiotic stress is severe environmental stress, which impairs crop production on irrigated land worldwide. Overall, the susceptibility or tolerance to the stress in plants is a coordinated action of multiple stress responsive genes, which also cross-talk with other components of stress signal transduction pathways. Plant responses to abiotic stress can be determined by the severity of the stress and by the metabolic status of the plant. Abscisic acid (ABA) is a phytohormone critical for plant growth and development and plays an important role in integrating various stress signals and controlling downstream stress responses. Plants have to adjust ABA levels constantly in responce to changing physiological and environmental conditions. To date, the mechanisms for fine-tuning of ABA levels remain elusive. The mechanisms by which plants respond to stress include both ABA-dependent and ABA-independent processes. Various transcription factors such as DREB2A/2B, AREB1, RD22BP1 and MYC/MYB are known to regulate the ABA-responsive gene expression through interacting with their corrosponding cis-acting elements such as DRE/CRT, ABRE and MYCRS/MYBRS, respectively. Understanding these mechanisms is important to improve stress tolerance in crops plants. This article first describes the general pathway for plant stress response followed by roles of ABA and transcription factors in stress tolerance including the regulation of ABA biosynthesis.

Abscisic Acid and Abiotic Stress Signaling

PubMed Central

2007-01-01

Abiotic stress is severe environmental stress, which impairs crop production on irrigated land worldwide. Overall, the susceptibility or tolerance to the stress in plants is a coordinated action of multiple stress responsive genes, which also cross-talk with other components of stress signal transduction pathways. Plant responses to abiotic stress can be determined by the severity of the stress and by the metabolic status of the plant. Abscisic acid (ABA) is a phytohormone critical for plant growth and development and plays an important role in integrating various stress signals and controlling downstream stress responses. Plants have to adjust ABA levels constantly in responce to changing physiological and environmental conditions. To date, the mechanisms for fine-tuning of ABA levels remain elusive. The mechanisms by which plants respond to stress include both ABA-dependent and ABA-independent processes. Various transcription factors such as DREB2A/2B, AREB1, RD22BP1 and MYC/MYB are known to regulate the ABA-responsive gene expression through interacting with their corrosponding cis-acting elements such as DRE/CRT, ABRE and MYCRS/MYBRS, respectively. Understanding these mechanisms is important to improve stress tolerance in crops plants. This article first describes the general pathway for plant stress response followed by roles of ABA and transcription factors in stress tolerance including the regulation of ABA biosynthesis. PMID:19516981

One-step synthesis of hybrid inorganic-organic nanocomposite coatings by novel laser adaptive ablation deposition technique

NASA Astrophysics Data System (ADS)

Serbezov, Valery; Sotirov, Sotir

2013-03-01

A novel approach for one-step synthesis of hybrid inorganic-organic nanocomposite coatings by new modification of Pulsed Laser Deposition technology called Laser Adaptive Ablation Deposition (LAAD) is presented. Hybrid nanocomposite coatings including Mg- Rapamycin and Mg- Desoximetasone were produced by UV TEA N2 laser under low vacuum (0.1 Pa) and room temperature onto substrates from SS 316L, KCl and NaCl. The laser fluence for Mg alloy was 1, 8 J/cm2 and for Desoximetasone 0,176 J/cm2 and for Rapamycin 0,118 J/cm2 were respectively. The threedimensional two-segmented single target was used to adapt the interaction of focused laser beam with inorganic and organic material. Magnesium alloy nanoparticles with sizes from 50 nm to 250 nm were obtained in organic matrices. The morphology of nanocomposites films were studied by Bright field / Fluorescence optical microscope and Scanning Electron Microscope (SEM). Fourier Transform Infrared (FTIR) spectroscopy measurements were applied in order to study the functional properties of organic component before and after the LAAD process. Energy Dispersive X-ray Spectroscopy (EDX) was used for identification of Mg alloy presence in hybrid nanocomposites coatings. The precise control of process parameters and particularly of the laser fluence adjustment enables transfer on materials with different physical chemical properties and one-step synthesis of complex inorganic- organic nanocomposites coatings.

Abiotic and Biotic Mechanisms Controlling In Situ Remediation of NDMA

DTIC Science & Technology

2009-05-01

FINAL REPORT Abiotic and Biotic Mechanisms Controlling In Situ Remediation of NDMA SERDP Project ER-1421 MAY 2009 James E. Szecsody...00-2009 4. TITLE AND SUBTITLE Abiotic and Biotic Mechanisms Controlling In Situ Remediation of NDMA 5a. CONTRACT NUMBER 5b. GRANT NUMBER 5c...investigate whether in situ coupled abiotic/biotic degradation of N-nitrosodimethylamine ( NDMA , an emerging contaminant) could be used as a permeable

Urinary bladder organ hypertrophy is partially regulated by Akt1-mediated protein synthesis pathway.

PubMed

Qiao, Li-Ya; Xia, Chunmei; Shen, Shanwei; Lee, Seong Ho; Ratz, Paul H; Fraser, Matthew O; Miner, Amy; Speich, John E; Lysiak, Jeffrey J; Steers, William D

2018-05-15

The present study aims to investigate the role of Akt in the regulation of urinary bladder organ hypertrophy caused by partial bladder outlet obstruction (pBOO). Male rats were surgically induced for pBOO. Real-time PCR and western blot were used to examine the levels of mRNA and protein. A phosphoinositide 3-kinase (PI3K) inhibitor LY294002 was used to inhibit the activity of endogenous Akt. The urinary bladder developed hypertrophy at 2 weeks of pBOO. The protein but not mRNA levels of type I collagen and α-smooth muscle actin (αSMA) were increased in pBOO bladder when compared to sham control. The phosphorylation (activation) levels of Akt1 (p-Ser 473 ), mammalian target of rapamycin (mTOR), p70S6 kinase (p70S6K), and 4E-BP1 were also increased in pBOO bladder. LY294002 treatment reduced the phosphorylation levels of Akt1 and 4E-BP1, and the protein levels of type I collagen and αSMA in pBOO bladder. The mRNA and protein levels of proliferating cell nuclear antigen (PCNA) were increased in pBOO bladder, and PCNA up-regulation occurred in urothelial not muscular layer. LY294002 treatment had no effect on the mRNA and protein levels of PCNA in pBOO bladder. LY294002 treatment partially reduced the bladder weight caused by pBOO. pBOO-induced urinary bladder hypertrophy is attributable to fibrosis, smooth muscle cellular hypertrophy, and urothelium cell hyper-proliferation. Akt1-mediated protein synthesis in pBOO bladder contributes to type I collagen and αSMA but not PCNA up-regulation. Target of Akt1 is necessary but not sufficient in treatment of urinary bladder hypertrophy following pBOO. Copyright © 2018 Elsevier Inc. All rights reserved.

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

NASA Astrophysics Data System (ADS)

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.

Synthesis of complex organic molecules in simulated methane rich astrophysical ices

NASA Astrophysics Data System (ADS)

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

2017-12-01

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.

The Potential Role of Formate for Synthesis and Life in Serpentinization Systems

NASA Astrophysics Data System (ADS)

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

2016-12-01

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.

Microfluidic approach toward continuous and ultrafast synthesis of metal-organic framework crystals and hetero structures in confined microdroplets.

PubMed

Faustini, Marco; Kim, Jun; Jeong, Guan-Young; Kim, Jin Yeong; Moon, Hoi Ri; Ahn, Wha-Seung; Kim, Dong-Pyo

2013-10-02

Herein, we report a novel nanoliter droplet-based microfluidic strategy for continuous and ultrafast synthesis of metal-organic framework (MOF) crystals and MOF heterostructures. Representative MOF structures, such as HKUST-1, MOF-5, IRMOF-3, and UiO-66, were synthesized within a few minutes via solvothermal reactions with substantially faster kinetics in comparison to the conventional batch processes. The approach was successfully extended to the preparation of a demanding Ru3BTC2 structure that requires high-pressure hydrothermal synthesis conditions. Finally, three different types of core-shell MOF composites, i.e., Co3BTC2@Ni3BTC2, MOF-5@diCH3-MOF-5, and Fe3O4@ZIF-8, were synthesized by exploiting a unique two-step integrated microfluidic synthesis scheme in a continuous-flow mode. The synthesized MOF crystals were characterized by X-ray diffraction, scanning electron microscopy, and BET surface area measurements. In comparison with bare MOF-5, MOF-5@diCH3-MOF-5 showed enhanced structural stability in the presence of moisture, and the catalytic performance of Fe3O4@ZIF-8 was examined using Knoevenagel condensation as a probe reaction. The microfluidic strategy allowed continuous fabrication of high-quality MOF crystals and composites exhibiting distinct morphological characteristics in a time-efficient manner and represents a viable alternative to the time-consuming and multistep MOF synthesis processes.

Synthesis of many different types of organic small molecules using one automated process.

PubMed

Li, Junqi; Ballmer, Steven G; Gillis, Eric P; Fujii, Seiko; Schmidt, Michael J; Palazzolo, Andrea M E; Lehmann, Jonathan W; Morehouse, Greg F; Burke, Martin D

2015-03-13

Small-molecule synthesis usually relies on procedures that are highly customized for each target. A broadly applicable automated process could greatly increase the accessibility of this class of compounds to enable investigations of their practical potential. Here we report the synthesis of 14 distinct classes of small molecules using the same fully automated process. This was achieved by strategically expanding the scope of a building block-based synthesis platform to include even C(sp3)-rich polycyclic natural product frameworks and discovering a catch-and-release chromatographic purification protocol applicable to all of the corresponding intermediates. With thousands of compatible building blocks already commercially available, many small molecules are now accessible with this platform. More broadly, these findings illuminate an actionable roadmap to a more general and automated approach for small-molecule synthesis. Copyright © 2015, American Association for the Advancement of Science.

Synthesis of Meso-Octamethylporphyrinogen: An Undergraduate Laboratory Mini-Scale Experiment in Organic Heterocyclic Chemistry

ERIC Educational Resources Information Center

Sobral, Abilio J. F. N.

2005-01-01

The synthesis of meso-octamethylporphyrinogen that involves a mini-scale preparation and uses acetone as reactant and also as solvent is presented. It results in a product of almost analytical grade directly from the reaction medium.

How does the general public view posthumous organ donation? A meta-synthesis of the qualitative literature

PubMed Central

2011-01-01

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 These findings afford

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

SciTech Connect

Le, Thu; Striolo, Alberto; Turner, C. Heath

An important scientific debate focuses on the possibility of abiotic synthesis of hydrocarbons during oceanic crust-seawater interactions. While on-site measurements near hydrothermal vents support this possibility, laboratory studies have provided data that are in some cases contradictory. At conditions relevant for sub-surface environments it has been shown that classic thermodynamics favour the production of CO 2 from CH 4, while abiotic methane synthesis would require the opposite. However, confinement effects are known to alter reaction equilibria. This report shows that indeed thermodynamic equilibrium can be shifted towards methane production, suggesting that thermal hydrocarbon synthesis near hydrothermal vents and deeper inmore » the magma-hydrothermal system is possible. We report reactive ensemble Monte Carlo simulations for the CO 2 methanation reaction. We compare the predicted equilibrium composition in the bulk gaseous phase to that expected in the presence of confinement. In the bulk phase we obtain excellent agreement with classic thermodynamic expectations. When the reactants can exchange between bulk and a confined phase our results show strong dependency of the reaction equilibrium conversions, X CO2, on nanopore size, nanopore chemistry, and nanopore morphology. Some physical conditions that could shift significantly the equilibrium composition of the reactive system with respect to bulk observations are discussed.« less

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

DOE PAGES

Le, Thu; Striolo, Alberto; Turner, C. Heath; ...

2017-08-21

An important scientific debate focuses on the possibility of abiotic synthesis of hydrocarbons during oceanic crust-seawater interactions. While on-site measurements near hydrothermal vents support this possibility, laboratory studies have provided data that are in some cases contradictory. At conditions relevant for sub-surface environments it has been shown that classic thermodynamics favour the production of CO 2 from CH 4, while abiotic methane synthesis would require the opposite. However, confinement effects are known to alter reaction equilibria. This report shows that indeed thermodynamic equilibrium can be shifted towards methane production, suggesting that thermal hydrocarbon synthesis near hydrothermal vents and deeper inmore » the magma-hydrothermal system is possible. We report reactive ensemble Monte Carlo simulations for the CO 2 methanation reaction. We compare the predicted equilibrium composition in the bulk gaseous phase to that expected in the presence of confinement. In the bulk phase we obtain excellent agreement with classic thermodynamic expectations. When the reactants can exchange between bulk and a confined phase our results show strong dependency of the reaction equilibrium conversions, X CO2, on nanopore size, nanopore chemistry, and nanopore morphology. Some physical conditions that could shift significantly the equilibrium composition of the reactive system with respect to bulk observations are discussed.« less

Organic synthesis in the Smith Group: a personal selection of a dozen lessons learned at the University of Pennsylvania.

PubMed

Minbiole, Kevin P C

2016-04-01

The passionate study of the complex and ever-evolving discipline of organic synthesis over more than a four-decade span is certain to elucidate meaningful and significant lessons. Over this period, Amos B. Smith III, the Rhodes-Thompson Professor of Chemistry and Member of the Monell Chemical Senses Center at the University of Pennsylvania, has mentored well over 100 doctoral and masters students, more than 200 postdoctoral associates and numerous undergraduates, in addition to collaborating with a wide spectrum of internationally recognized scholars. His research interests, broadly stated, comprise complex molecule synthesis, the development of new, versatile and highly effective synthetic methods, bioorganic and medicinal chemistry, peptide mimicry chemistry and material science. Each area demands a high level of synthetic design and execution. United by a passion to unlock the secrets of organic synthesis, and perhaps of Nature itself, innumerable lessons have been, and continue to be, learned by the members of the Smith Group. This lead article in a Special Issue of the Journal of Antibiotics affords an opportunity to share some of those lessons learned, albeit a small selection of personal favorites.

Generation of RNA in abiotic conditions.

NASA Astrophysics Data System (ADS)

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

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

NASA Astrophysics Data System (ADS)

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.

2017-07-01

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.

Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

PubMed Central

2016-01-01

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

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

PubMed

Kent, Stephen B H

2013-11-11

Erythropoietin, commonly known as EPO, is a glycoprotein hormone that stimulates the production of red blood cells. Recombinant EPO has been described as "arguably the most successful drug spawned by the revolution in recombinant DNA technology". Recently, the EPO glycoprotein molecule has re-emerged as a major target of synthetic organic chemistry. In this article I will give an account of an important body of earlier work on the chemical synthesis of a designed EPO analogue that had full biological activity and improved pharmacokinetic properties. The design and synthesis of this "synthetic erythropoiesis protein" was ahead of its time, but has gained new relevance in recent months. Here I will document the story of one of the major accomplishments of synthetic chemistry in a more complete way than is possible in the primary literature, and put the work in its contemporaneous context. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Solvent-Assisted Linker Exchange: An Alternative to the De Novo Synthesis of Unattainable Metal-Organic Frameworks

SciTech Connect

Karagiaridi, Olga; Bury, Wojciech; Mondloch, Joseph E.

Metal-organic frameworks (MOFs) have gained considerable attention as hybrid materials—in part because of a multitude of potential useful applications, ranging from gas separation to catalysis and light harvesting. Unfortunately, de novo synthesis of MOFs with desirable function–property combinations is not always reliable and may suffer from vagaries such as formation of undesirable topologies, low solubility of precursors, and loss of functionality of the sensitive network components. The recently discovered synthetic approach coined solvent-assisted linker exchange (SALE) constitutes a simple to implement strategy for circumventing these setbacks; its use has already led to the generation of a variety of MOF materialsmore » previously unobtainable by direct synthesis methods. This Review provides a perspective of the achievements in MOF research that have been made possible with SALE and examines the studies that have facilitated the understanding and broadened the scope of use of this invaluable synthetic tool.« less

Two-dimensional parallel array technology as a new approach to automated combinatorial solid-phase organic synthesis

PubMed

Brennan; Biddison; Frauendorf; Schwarcz; Keen; Ecker; Davis; Tinder; Swayze

1998-01-01

An automated, 96-well parallel array synthesizer for solid-phase organic synthesis has been designed and constructed. The instrument employs a unique reagent array delivery format, in which each reagent utilized has a dedicated plumbing system. An inert atmosphere is maintained during all phases of a synthesis, and temperature can be controlled via a thermal transfer plate which holds the injection molded reaction block. The reaction plate assembly slides in the X-axis direction, while eight nozzle blocks holding the reagent lines slide in the Y-axis direction, allowing for the extremely rapid delivery of any of 64 reagents to 96 wells. In addition, there are six banks of fixed nozzle blocks, which deliver the same reagent or solvent to eight wells at once, for a total of 72 possible reagents. The instrument is controlled by software which allows the straightforward programming of the synthesis of a larger number of compounds. This is accomplished by supplying a general synthetic procedure in the form of a command file, which calls upon certain reagents to be added to specific wells via lookup in a sequence file. The bottle position, flow rate, and concentration of each reagent is stored in a separate reagent table file. To demonstrate the utility of the parallel array synthesizer, a small combinatorial library of hydroxamic acids was prepared in high throughput mode for biological screening. Approximately 1300 compounds were prepared on a 10 μmole scale (3-5 mg) in a few weeks. The resulting crude compounds were generally >80% pure, and were utilized directly for high throughput screening in antibacterial assays. Several active wells were found, and the activity was verified by solution-phase synthesis of analytically pure material, indicating that the system described herein is an efficient means for the parallel synthesis of compounds for lead discovery. Copyright 1998 John Wiley & Sons, Inc.

Natural abiotic formation of oxalic acid in soils: results from aromatic model compounds and soil samples.

PubMed

Studenroth, Sabine; Huber, Stefan G; Kotte, Karsten; Schöler, Heinz F

2013-02-05

Oxalic acid is the smallest dicarboxylic acid and plays an important role in soil processes (e.g., mineral weathering and metal detoxification in plants). We have first proven its abiotic formation in soils and investigated natural abiotic degradation processes based on the oxidation of soil organic matter, enhanced by Fe(3+) and H(2)O(2) as hydroxyl radical suppliers. Experiments with the model compound catechol and further hydroxylated benzenes were performed to examine a common degradation pathway and to presume a general formation mechanism of oxalic acid. Two soil samples were tested for the release of oxalic acid and the potential effects of various soil parameters on oxalic acid formation. Additionally, the soil samples were treated with different soil sterilization methods to prove the oxalic acid formation under abiotic soil conditions. Different series of model experiments were conducted to determine a range of factors including Fe(3+), H(2)O(2), reaction time, pH, and chloride concentration on oxalic acid formation. Under certain conditions, catechol is degraded up to 65.6% to oxalic acid referring to carbon. In serial experiments with two soil samples, oxalic acid was produced, and the obtained results are suggestive of an abiotic degradation process. In conclusion, Fenton-like conditions with low Fe(3+) concentrations and an excess of H(2)O(2) as well as acidic conditions were required for an optimal oxalic acid formation. The presence of chloride reduced oxalic acid formation.

Massive production of abiotic methane during subduction evidenced in metamorphosed ophicarbonates from the Italian Alps

PubMed Central

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

2017-01-01

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. PMID:28223715

Alternative Splicing Control of Abiotic Stress Responses.

PubMed

Laloum, Tom; Martín, Guiomar; Duque, Paula

2018-02-01

Alternative splicing, which generates multiple transcripts from the same gene, is an important modulator of gene expression that can increase proteome diversity and regulate mRNA levels. In plants, this post-transcriptional mechanism is markedly induced in response to environmental stress, and recent studies have identified alternative splicing events that allow rapid adjustment of the abundance and function of key stress-response components. In agreement, plant mutants defective in splicing factors are severely impaired in their response to abiotic stress. Notably, mounting evidence indicates that alternative splicing regulates stress responses largely by targeting the abscisic acid (ABA) pathway. We review here current understanding of post-transcriptional control of plant stress tolerance via alternative splicing and discuss research challenges for the near future. Copyright © 2017 Elsevier Ltd. All rights reserved.

Abiotic Stress Resistance, a Novel Moonlighting Function of Ribosomal Protein RPL44 in the Halophilic Fungus Aspergillus glaucus

PubMed Central

Liu, Xiao-Dan; Xie, Lixia; Wei, Yi; Zhou, Xiaoyang; Jia, Baolei; Liu, Jinliang

2014-01-01

Ribosomal proteins are highly conserved components of basal cellular organelles, primarily involved in the translation of mRNA leading to protein synthesis. However, certain ribosomal proteins moonlight in the development and differentiation of organisms. In this study, the ribosomal protein L44 (RPL44), associated with salt resistance, was screened from the halophilic fungus Aspergillus glaucus (AgRPL44), and its activity was investigated in Saccharomyces cerevisiae and Nicotiana tabacum. Sequence alignment revealed that AgRPL44 is one of the proteins of the large ribosomal subunit 60S. Expression of AgRPL44 was upregulated via treatment with salt, sorbitol, or heavy metals to demonstrate its response to osmotic stress. A homologous sequence from the model fungus Magnaporthe oryzae, MoRPL44, was cloned and compared with AgRPL44 in a yeast expression system. The results indicated that yeast cells with overexpressed AgRPL44 were more resistant to salt, drought, and heavy metals than were yeast cells expressing MoRPL44 at a similar level of stress. When AgRPL44 was introduced into M. oryzae, the transformants displayed obviously enhanced tolerance to salt and drought, indicating the potential value of AgRPL44 for genetic applications. To verify the value of its application in plants, tobacco was transformed with AgRPL44, and the results were similar. Taken together, we conclude that AgRPL44 supports abiotic stress resistance and may have value for genetic application. PMID:24814782

ABIOTIC IN SITU TECHNOLOGIES FOR GROUNDWATER REMEDIATION CONFERENCE: PROCEEDINGS

EPA Science Inventory

The USEPA conference on Abiotic In Situ Technologies for Groundwater Remediation was held in Dallas, TX, 8/31-9/2/99. The goal of the meeting was to disseminate current information on abiotic in situ groundwater treatment echnologies. Although much information is being provided a...

A significant abiotic pathway for the formation of unknown nitrogen in nature

NASA Astrophysics Data System (ADS)

Jokic, A.; Schulten, H.-R.; Cutler, J. N.; Schnitzer, M.; Huang, P. M.

2004-03-01

The global nitrogen cycle is of prime importance in natural ecosystems. However, the origin and nature of up to one-half of total soil N remains obscure despite all attempts at elucidation. Our data provide, for the first time, unequivocal evidence that the promoting action of Mn (IV) oxide on the Maillard reaction (sugar-amino acid condensation) under ambient conditions results in the abiotic formation of heterocyclic N compounds, which are often referred to as unknown nitrogen, and of amides which are apparently the dominant N moieties in nature. The information presented is of fundamental significance in understanding the role of mineral colloids in abiotic transformations of organic N moieties, the incorporation of N in the organic matrix of fossil fuels, and the global N cycle.

Colloidal Synthesis of CH3 NH3 PbBr3 Nanoplatelets with Polarized Emission through Self-Organization.

PubMed

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

2017-02-06

We report a combined experimental and theoretical study of the synthesis of CH 3 NH 3 PbBr 3 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 CH 3 NH 3 PbBr 3 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 CH 3 NH 3 PbBr 3 nanoplatelets exhibit excellent polarized emissions for stretched CH 3 NH 3 PbBr 3 nanoplatelets embedded in a polymer composite film, showing advantageous photoluminescence properties for display backlights. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

NASA Astrophysics Data System (ADS)

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

MicroRNAs As Potential Targets for Abiotic Stress Tolerance in Plants

PubMed Central

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

2016-01-01

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

Three new europium(III) methanetriacetate metal-organic frameworks: the influence of synthesis on the product topology.

PubMed

Cañadillas-Delgado, Laura; Fabelo, Oscar; Pasán, Jorge; Déniz, Mariadel; Martínez-Benito, Carla; Díaz-Gallifa, Pau; Martín, Tomás; Ruiz-Pérez, Catalina

2014-02-01

Three new metal-organic framework structures containing Eu(III) and the little explored methanetriacetate (C7H7O6(3-), mta(3-)) ligand have been synthesized. Gel synthesis yields a two-dimensional framework with the formula [Eu(mta)(H2O)3]n·2nH2O, (I), while two polymorphs of the three-dimensional framework material [Eu(mta)(H2O)]n·nH2O, (II) and (III), are obtained through hydrothermal synthesis at either 423 or 443 K. Compounds (I) and (II) are isomorphous with previously reported Gd(III) compounds, but compound (III) constitutes a new phase. Compound (I) can be described in terms of dinuclear [Eu2(H2O)4](6+) units bonded through mta(3-) ligands to form a two-dimensional framework with topology corresponding to a (6,3)-connected binodal (4(3))(4(6)6(6)8(3))-kgd net, where the dinuclear [Eu2(H2O)4](6+) units are considered as a single node. Compounds (II) and (III) have distinct three-dimensional topologies, namely a (4(12)6(3))(4(9)6(6))-nia net for (II) and a (4(10)6(5))(4(11)6(4))-K2O2; 36641 net for (III). The crystal density of (III) is greater than that of (II), consistent with the increase of temperature, and thereby autogeneous pressure, in the hydrothermal synthesis.

Use of organic precursors and graphenes in the controlled synthesis of carbon-containing nanomaterials for energy storage and conversion.

PubMed

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

2013-01-15

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

Synthesis of the Anticonvulsant Drug 5,5-Diphenylhydantoin: An Undergraduate Organic Chemistry Experiment.

ERIC Educational Resources Information Center

Hayward, Rodney C.

1983-01-01

Hydantoins are a drug family lying within the broadly related ureide structural frame which encompasses many of the anticonvulsant drugs used in treatment of various types of epilepsy. Background information and experimental procedures are provided for the synthesis of the hydantoin 5,5-diphenylhydantoin. (JN)

A Green, Enantioselective Synthesis of Warfarin for the Undergraduate Organic Laboratory

ERIC Educational Resources Information Center

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

2010-01-01

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…

Student-Fabricated Microfluidic Devices as Flow Reactors for Organic and Inorganic Synthesis

ERIC Educational Resources Information Center

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

2015-01-01

Flow synthesis in microfluidic devices has been rapidly adapted in the pharmaceutical industry and in many research laboratories. Yet, the cost of commercial flow reactors is a major factor limiting the dissemination of this technology in the undergraduate curriculum. Here, we present a laboratory activity where students design and fabricate…

A Multistep Synthesis Featuring Classic Carbonyl Chemistry for the Advanced Organic Chemistry Laboratory

ERIC Educational Resources Information Center

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

2012-01-01

A multistep synthesis of 5-isopropyl-1,3-cyclohexanedione is carried out from three commodity chemicals. The sequence involves an aldol condensation, Dieckmann-type annulation, ester hydrolysis, and decarboxylation. No purification is required until after the final step, at which point gravity column chromatography provides the desired product in…

SYNTHESIS OF MIXED FULL AND SEMIESTERS OF PHOSPHOROUS ACID AS ORGANIC MOTOR OIL ADDITIVES,

DTIC Science & Technology

The synthesis of mixed full and semiesters of phosphonic acid was effected using alkylphenols produced by the chemical industry. By condensation of...industrial alkylphenol or the condensation of acid chloride of di-(alkylphenyl)-phosphorous acid with diethylamine, the corresponding mixed full and semiesters

In situ synthesis of fluorescent magnetosomes using an organic membrane as a soft template.

PubMed

Ke, Wenjing; Zhang, Juhua; An, Xueqin; Zhang, Bo

2017-05-04

A novel approach was presented for the in situ synthesis of fluorescent magnetosomes by biological mineralization and carbonization processes for the first time. The surface structures, magnetism and fluorescence were studied, and the cytotoxicity tests and fluorescent trace in liposomes were probed. The fluorescent magnetosomes exhibit not only unique fluorescence and ferromagnetic properties but also low toxicity and superior imaging capability.

Soft templating strategies for the synthesis of mesoporous materials: inorganic, organic-inorganic hybrid and purely organic solids.

PubMed

Pal, Nabanita; Bhaumik, Asim

2013-03-01

With the discovery of MCM-41 by Mobil researchers in 1992 the journey of the research on mesoporous materials started and in the 21st century this area of scientific investigation have extended into numerous branches, many of which contribute significantly in emerging areas like catalysis, energy, environment and biomedical research. As a consequence thousands of publications came out in large varieties of national and international journals. In this review, we have tried to summarize the published works on various synthetic pathways and formation mechanisms of different mesoporous materials viz. inorganic, organic-inorganic hybrid and purely organic solids via soft templating pathways. Generation of nanoscale porosity in a solid material usually requires participation of organic template (more specifically surfactants and their supramolecular assemblies) called structure-directing agent (SDA) in the bottom-up chemical reaction process. Different techniques employed for the syntheses of inorganic mesoporous solids, like silicas, metal doped silicas, transition and non-transition metal oxides, mixed oxides, metallophosphates, organic-inorganic hybrids as well as purely organic mesoporous materials like carbons, polymers etc. using surfactants are depicted schematically and elaborately in this paper. Moreover, some of the frontline applications of these mesoporous solids, which are directly related to their functionality, composition and surface properties are discussed at the appropriate places. Copyright © 2012 Elsevier B.V. All rights reserved.

Particle size studies to reveal crystallization mechanisms of the metal organic framework HKUST-1 during sonochemical synthesis.

PubMed

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

2017-01-01

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.

Abiotic stress and the plant circadian clock

PubMed Central

Sanchez, Alfredo; Shin, Jieun

2011-01-01

In this review, we focus on the interaction between the circadian clock of higher plants to that of metabolic and physiological processes that coordinate growth and performance under a predictable, albeit changing environment. In this, the phytochrome and cryptochrome photoreceptors have shown to be important, but not essential for oscillator control under diurnal cycles of light and dark. From this foundation, we will examine how emerging findings have firmly linked the circadian clock, as a central mediator in the coordination of metabolism, to maintain homeostasis. This occurs by oscillator synchronization of global transcription, which leads to a dynamic control of a host of physiological processes. These include the determination of the levels of primary and secondary metabolites, and the anticipation of future environmental stresses, such as mid-day drought and midnight coldness. Interestingly, metabolic and stress cues themselves appear to feedback on oscillator function. In such a way, the circadian clock of plants and abiotic-stress tolerance appear to be firmly interconnected processes. PMID:21325898

The "Virtual ChemLab" Project: A Realistic and Sophisticated Simulation of Organic Synthesis and Organic Qualitative Analysis

ERIC Educational Resources Information Center

Woodfield, Brian F.; Andrus, Merritt B.; Waddoups, Gregory L.; Moore, Melissa S.; Swan, Richard; Allen, Rob; Bodily, Greg; Andersen, Tricia; Miller, Jordan; Simmons, Bryon; Stanger, Richard

2005-01-01

A set of sophisticated and realistic laboratory simulations is created for use in freshman- and sophomore-level chemistry classes and laboratories called 'Virtual ChemLab'. A detailed assessment of student responses is provided and the simulation's pedagogical utility is described using the organic simulation.

Recent Molecular Advances on Downstream Plant Responses to Abiotic Stress

PubMed Central

dos Reis, Sávio Pinho; Lima, Aline Medeiros; de Souza, Cláudia Regina Batista

2012-01-01

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. PMID:22942725

Biocatalytic organic synthesis of optically pure (S)-scoulerine and berbine and benzylisoquinoline alkaloids.

PubMed

Schrittwieser, Joerg H; Resch, Verena; Wallner, Silvia; Lienhart, Wolf-Dieter; Sattler, Johann H; Resch, Jasmin; Macheroux, Peter; Kroutil, Wolfgang

2011-08-19

A chemoenzymatic approach for the asymmetric total synthesis of the title compounds is described that employs an enantioselective oxidative C-C bond formation catalyzed by berberine bridge enzyme (BBE) in the asymmetric key step. This unique reaction yielded enantiomerically pure (R)-benzylisoquinoline derivatives and (S)-berbines such as the natural product (S)-scoulerine, a sedative and muscle relaxing agent. The racemic substrates rac-1 required for the biotransformation were prepared in 4-8 linear steps using either a Bischler-Napieralski cyclization or a C1-Cα alkylation approach. The chemoenzymatic synthesis was applied to the preparation of fourteen enantiomerically pure alkaloids, including the natural products (S)-scoulerine and (R)-reticuline, and gave overall yields of up to 20% over 5-9 linear steps.

An Introduction to Zeolite Synthesis Using Imidazolium-Based Cations as Organic Structure-Directing Agents.

PubMed

Vinaches, Paloma; Bernardo-Gusmão, Katia; Pergher, Sibele B C

2017-08-06

Zeolite synthesis is a wide area of study with increasing popularity. Several general reviews have already been published, but they did not summarize the study of imidazolium species in zeolite synthesis. Imidazolium derivatives are promising compounds in the search for new zeolites and can be used to help understand the structure-directing role. Nearly 50 different imidazolium cations have already been used, resulting in a variety of zeolitic types, but there are still many derivatives to be studied. In this context, the purpose of this short review is to help researchers starting in this area by summarizing the most important concepts related to imidazolium-based zeolite studies and by presenting a table of recent imidazolium derivatives that have been recently studied to facilitate filling in the knowledge gaps.

Controlled iterative cross-coupling: on the way to the automation of organic synthesis.

PubMed

Wang, Congyang; Glorius, Frank

2009-01-01

Repetition does not hurt! New strategies for the modulation of the reactivity of difunctional building blocks are discussed, allowing the palladium-catalyzed controlled iterative cross-coupling and, thus, the efficient formation of complex molecules of defined size and structure (see scheme). As in peptide synthesis, this development will enable the automation of these reactions. M(PG)=protected metal, M(act)=metal.

Use of protein cages as a template for confined synthesis of inorganic and organic nanoparticles.

PubMed

Uchida, Masaki; Qazi, Shefah; Edwards, Ethan; Douglas, Trevor

2015-01-01

Protein cages are hollow spherical proteins assembled from a defined number of subunits. Because they are extremely homogeneous in size and structure, their interior cavities can serve as ideal templates to encapsulate and synthesize well-defined nanoparticles. Here, we describe the exemplary synthesis of a hard and a soft material in two representative protein cages, i.e., magnetite nanoparticles in ferritin and a poly(2-aminoethyl)methacrylate inside a viral capsid derived from the bacteriophage P22.

Synthesis and Structure of Fully Conjugated Block Copolymers Utilized in Organic Photovoltaics

NASA Astrophysics Data System (ADS)

Lee, Youngmin; Aplan, Melissa; Wang, Qing; Gomez, Enrique D.

2015-03-01

Fully conjugated block copolymers have the potential to overcome many of the limitations of mixtures and blends as photoactive layers in solar cells; furthermore, they may serve as model systems to study fundamental questions regarding optoelectric properties and charge transfer. However, the synthesis of fully conjugated block copolymers remains a challenging issue in the fieldchallenge. We have optimized the two-step synthesis of P3HT-b-PFTBT, which is composed comprised of Grignard metathesis for polymerization of P3HT followed by chain extension through a Suzuki-Miyaura polycondenstation. We find that the concentration of the Grignard reagent is critical for end-group control such that P3HT is terminated by H at one end and Br at the other. Furthermore, we can utilize an asymmetric feed ratio of monomers for the Suzuki-Miyaura reaction to minimize the amount of uncoupled homopolymers and to control the molecular weight of the second block. We investigated the chemical composition, structure and electrical characteristics of the polymers prepared by the different synthetic methods, and demonstrate that we can utilize these strategies for the synthesis of block copolymers beyond P3HT-b-PFTBT.

Synthesis and morphogenesis of organic and inorganic polymers by means of biominerals and biomimetic materials.

PubMed

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

2013-02-11

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.

The Ascorbate-glutathione-α-tocopherol Triad in Abiotic Stress Response

PubMed Central

Szarka, András; Tomasskovics, Bálint; Bánhegyi, Gábor

2012-01-01

The life of any living organism can be defined as a hurdle due to different kind of stresses. As with all living organisms, plants are exposed to various abiotic stresses, such as drought, salinity, extreme temperatures and chemical toxicity. These primary stresses are often interconnected, and lead to the overproduction of reactive oxygen species (ROS) in plants, which are highly reactive and toxic and cause damage to proteins, lipids, carbohydrates and DNA, which ultimately results in oxidative stress. Stress-induced ROS accumulation is counteracted by enzymatic antioxidant systems and non-enzymatic low molecular weight metabolites, such as ascorbate, glutathione and α-tocopherol. The above mentioned low molecular weight antioxidants are also capable of chelating metal ions, reducing thus their catalytic activity to form ROS and also scavenge them. Hence, in plant cells, this triad of low molecular weight antioxidants (ascorbate, glutathione and α-tocopherol) form an important part of abiotic stress response. In this work we are presenting a review of abiotic stress responses connected to these antioxidants. PMID:22605990

A focus on natural variation for abiotic constraints response in the model species Arabidopsis thaliana.

PubMed

Lefebvre, Valérie; Kiani, Seifollah Poormohammad; Durand-Tardif, Mylène

2009-08-13

Plants are particularly subject to environmental stress, as they cannot move from unfavourable surroundings. As a consequence they have to react in situ. In any case, plants have to sense the stress, then the signal has to be transduced to engage the appropriate response. Stress response is effected by regulating genes, by turning on molecular mechanisms to protect the whole organism and its components and/or to repair damage. Reactions vary depending on the type of stress and its intensity, but some are commonly turned on because some responses to different abiotic stresses are shared. In addition, there are multiple ways for plants to respond to environmental stress, depending on the species and life strategy, but also multiple ways within a species depending on plant variety or ecotype. It is regularly accepted that populations of a single species originating from diverse geographic origins and/or that have been subjected to different selective pressure, have evolved retaining the best alleles for completing their life cycle. Therefore, the study of natural variation in response to abiotic stress, can help unravel key genes and alleles for plants to cope with their unfavourable physical and chemical surroundings. This review is focusing on Arabidopsis thaliana which has been largely adopted by the global scientific community as a model organism. Also, tools and data that facilitate investigation of natural variation and abiotic stress encountered in the wild are set out. Characterization of accessions, QTLs detection and cloning of alleles responsible for variation are presented.

Primordial soup was edible: abiotically produced Miller-Urey mixture supports bacterial growth.

PubMed

Xie, Xueshu; Backman, Daniel; Lebedev, Albert T; Artaev, Viatcheslav B; Jiang, Liying; Ilag, Leopold L; Zubarev, Roman A

2015-09-28

Sixty years after the seminal Miller-Urey experiment that abiotically produced a mixture of racemized amino acids, we provide a definite proof that this primordial soup, when properly cooked, was edible for primitive organisms. Direct admixture of even small amounts of Miller-Urey mixture strongly inhibits E. coli bacteria growth due to the toxicity of abundant components, such as cyanides. However, these toxic compounds are both volatile and extremely reactive, while bacteria are highly capable of adaptation. Consequently, after bacterial adaptation to a mixture of the two most abundant abiotic amino acids, glycine and racemized alanine, dried and reconstituted MU soup was found to support bacterial growth and even accelerate it compared to a simple mixture of the two amino acids. Therefore, primordial Miller-Urey soup was perfectly suitable as a growth media for early life forms.

daf-16/FoxO promotes gluconeogenesis and trehalose synthesis during starvation to support survival

PubMed Central

Hibshman, Jonathan D; Doan, Alexander E; Moore, Brad T; Kaplan, Rebecca EW; Hung, Anthony; Webster, Amy K; Bhatt, Dhaval P; Chitrakar, Rojin; Hirschey, Matthew D

2017-01-01

daf-16/FoxO is required to survive starvation in Caenorhabditis elegans, but how daf-16IFoxO promotes starvation resistance is unclear. We show that daf-16/FoxO restructures carbohydrate metabolism by driving carbon flux through the glyoxylate shunt and gluconeogenesis and into synthesis of trehalose, a disaccharide of glucose. Trehalose is a well-known stress protectant, capable of preserving membrane organization and protein structure during abiotic stress. Metabolomic, genetic, and pharmacological analyses confirm increased trehalose synthesis and further show that trehalose not only supports survival as a stress protectant but also serves as a glycolytic input. Furthermore, we provide evidence that metabolic cycling between trehalose and glucose is necessary for this dual function of trehalose. This work demonstrates that daf-16/FoxO promotes starvation resistance by shifting carbon metabolism to drive trehalose synthesis, which in turn supports survival by providing an energy source and acting as a stress protectant. PMID:29063832

daf-16/FoxO promotes gluconeogenesis and trehalose synthesis during starvation to support survival.

PubMed

Hibshman, Jonathan D; Doan, Alexander E; Moore, Brad T; Kaplan, Rebecca Ew; Hung, Anthony; Webster, Amy K; Bhatt, Dhaval P; Chitrakar, Rojin; Hirschey, Matthew D; Baugh, L Ryan

2017-10-24

daf-16 /FoxO is required to survive starvation in Caenorhabditis elegans , but how daf-16I FoxO promotes starvation resistance is unclear. We show that daf-16 /FoxO restructures carbohydrate metabolism by driving carbon flux through the glyoxylate shunt and gluconeogenesis and into synthesis of trehalose, a disaccharide of glucose. Trehalose is a well-known stress protectant, capable of preserving membrane organization and protein structure during abiotic stress. Metabolomic, genetic, and pharmacological analyses confirm increased trehalose synthesis and further show that trehalose not only supports survival as a stress protectant but also serves as a glycolytic input. Furthermore, we provide evidence that metabolic cycling between trehalose and glucose is necessary for this dual function of trehalose. This work demonstrates that daf-16 /FoxO promotes starvation resistance by shifting carbon metabolism to drive trehalose synthesis, which in turn supports survival by providing an energy source and acting as a stress protectant.

Origin of Abiotic Methane in Submarine Hydrothermal Systems

NASA Astrophysics Data System (ADS)

Seewald, J. S.; German, C. R.; Grozeva, N. G.; Klein, F.; McDermott, J. M.; Ono, S.; Reeves, E. P.; Wang, D. T.

2018-05-01

Results of recent investigations into the chemical and isotopic composition of actively venting submarine hydrothermal fluids and volatile species trapped in fluid inclusions will be discussed in the context of processes responsible for abiotic CH4 formation.

Olivine Weathering: Abiotic Versus Biotic Processes as Possible Biosignatures

NASA Technical Reports Server (NTRS)

Longazo, T. G.; Wentworth, S. J.; McKay, D. S.; Southam, G.; Clemett, S. J.

2001-01-01

A preliminary study to determine how abiotic versus biotic processes affect the weathering of olivine crystals. Perhaps the differences between these weathering processes could be used as biosignatures. Additional information is contained in the original extended abstract.

Roles of melatonin in abiotic stress resistance in plants.

PubMed

Zhang, Na; Sun, Qianqian; Zhang, Haijun; Cao, Yunyun; Weeda, Sarah; Ren, Shuxin; Guo, Yang-Dong

2015-02-01

In recent years melatonin has emerged as a research highlight in plant studies. Melatonin has different functions in many aspects of plant growth and development. The most frequently mentioned functions of melatonin are related to abiotic stresses such as drought, radiation, extreme temperature, and chemical stresses. This review mainly focuses on the regulatory effects of melatonin when plants face harsh environmental conditions. Evidence indicates that environmental stress can increase the level of endogenous melatonin in plants. Overexpression of the melatonin biosynthetic genes elevates melatonin levels in transgenic plants. The transgenic plants show enhanced tolerance to abiotic stresses. Exogenously applied melatonin can also improve the ability of plants to tolerate abiotic stresses. The mechanisms by which melatonin alleviates abiotic stresses are discussed. © The Author 2014. Published by Oxford University Press on behalf of the Society for Experimental Biology. All rights reserved. For permissions, please email: journals.permissions@oup.com.

Nucleotide Selectivity in Abiotic RNA Polymerization Reactions.

PubMed

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

2017-09-01

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.

Nucleotide Selectivity in Abiotic RNA Polymerization Reactions

NASA Astrophysics Data System (ADS)

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

2017-09-01

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.

Voluntary Organizations and Community Groups as New Partners in Diabetes Self-management and Education: A Critical Interpretative Synthesis.

PubMed

Portillo, Mari Carmen; Regaira, Elena; Pumar-Méndez, María J; Mujika, Agurtzane; Vassilev, Ivaylo; Rogers, Anne; Wensing, Michel; Foss, Christina; Ruud Knutsen, Ingrid; Todorova, Elka; Roukova, Poli; Kennedy, Anne; Serrano, Manuel; Lionis, Christos; Angelaki, Agapi; Patelarou, Evridiki; Koetsenruijter, Jan

2015-10-01

The purpose of this study is to critically review the literature on the role and work of voluntary organizations and community groups and volunteers in diabetes self-management programs. It seeks to explain how these organizations are located and could be integrated further within a broader system of support. A critical interpretative synthesis of the literature was undertaken as part of the conceptual development of a European research project. Evidence (2000-November 2014) was searched in databases, with the use of key terms, and limited to the languages of the participating countries. This was supplemented by an additional hand search and snowballing technique. A total of 21 articles were included in the review. Evidence regarding the involvement of voluntary organizations in diabetes self-management programs mainly related to: the nature and remit of their work, responsibilities, and attributes; key strategies of programs accounting for success; motivations/barriers for engaging in volunteering participation; relationships between volunteers and users; and connections/tensions with formal services. This review has uncovered a range of facets of voluntary organizations and community groups relevant for supporting diabetes self-management such as the context within which they act and the nature of relationships developed with community and health services. The principles of "assistance, support, sharing, and link" seem essential for this voluntary initiative in self-management to establish effective reciprocal collaboration with health professionals. © 2015 The Author(s).

The Real Difference between Biotic and Abiotic Methane

NASA Astrophysics Data System (ADS)

Cao, X.; Bao, H.; Peng, Y.

2017-12-01

Methane has both biotic and abiotic origins, and the identification of these two origins has important implications not only in understanding terrestrial processes but also in searching for extraterrestrial life. Carbon and hydrogen isotopes in methane have been used to identify certain biosignatures, but such efforts often suffer from ambiguity. Recent advancement in our capability in measuring multiply substituted isotopologues of methane (i.e. 13CDH3 and 12CD2H2) has found large 12CD2H2 depletion in abiotic methane. Quantum tunneling has been proposed to account for the apparent abiotic signature. However, quantum tunneling is neither unique to abiotic processes nor consistent with the observed not-so-depleted hydrogen isotope composition. Here we constructed a general kinetic model for methane formation from CO2, and validated it by fitting its parameters to observed 13CDH3, 12CD2H2, and 12CDH3. Our model revealed that the fundamental difference between biotic and abiotic methane isotopic signatures is in the source of hydrogens during methane formation. Hydrogens in biotic methane originate from the stronger carbon-hydrogen and sulfur-hydrogen bonds, while hydrogens in abiotic methane originate from the much weaker metal-hydrogen adsorption bond. This hydrogen source difference results in abiotic methane being more depleted in 12CD2H2 than the biotic one. Our model also shows that the primary kinetic hydrogen isotope effect is at approximately 0.6 for both abiotic and biotic pathways, a normal value further nullifying the role of quantum tunneling. The active and exclusive shuttling of reduced hydrogen via strong chemical bonds like carbon-hydrogen and sulfur-hydrogen in coenzymes is proposed here to be a unique signature of life. In an ironic sense, it is the equilibrated hydrogen isotope composition in the hydrogen donors that distinguishes the living from the non-living.

Atmospheric Prebiotic Chemistry and Organic Hazes

PubMed Central

Trainer, Melissa G.

2013-01-01

Earth’s atmospheric composition at the time of the origin of life is not known, but it has often been suggested that chemical transformation of reactive species in the atmosphere was a significant source of prebiotic organic molecules. Experimental and theoretical studies over the past half century have shown that atmospheric synthesis can yield molecules such as amino acids and nucleobases, but these processes are very sensitive to gas composition and energy source. Abiotic synthesis of 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. PMID:24143126

Atmospheric Prebiotic Chemistry and Organic Hazes.

PubMed

Trainer, Melissa G

2013-08-01

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

Atmospheric Prebiotic Chemistry and Organic Hazes

NASA Technical Reports Server (NTRS)

Trainer, Melissa G.

2012-01-01

Earth's atmospheric composition at the time of the origin of life is not known, but it has often been suggested that chemical transformation of reactive species in the atmosphere was a significant source of pre biotic organic molecules. Experimental and theoretical studies over the past half century have shown that atmospheric synthesis can yield molecules such as amino acids and nucleobases, but these processes are very sensitive to gas composition and energy source. Abiotic synthesis of organic molecules is more productive in reduced atmospheres, yet the primitive Earth may not have been as reducing as earlier workers assumed, and recent research has reflected this shift in thinking. This work provides a survey of the range of chemical products that can be produced given a set of atmospheric conditions, with a particular focus on recent reports. Intertwined with the discussion of atmospheric synthesis is the consideration of an organic haze layer, which has been suggested as a possible ultraviolet shield on the anoxic early Earth. Since such a haze layer - if formed - would serve as a reservoir for organic molecules, the chemical composition of the aerosol should be closely examined. The results highlighted here show that a variety of products can be formed in mildly reducing or even neutral atmospheres, demonstrating that contributions of atmospheric synthesis to the organic inventory on early Earth should not be discounted. This review intends to bridge current knowledge of the range of possible atmospheric conditions in the prebiotic environment and pathways for synthesis under such conditions by examining the possible products of organic chemistry in the early atmosphere.

Ultraviolet-gas phase and -photocatalytic synthesis from CO and NH3. [photolysis products

NASA Technical Reports Server (NTRS)

Hubbard, J. S.; Voecks, G. E.; Hobby, G. L.; Ferris, J. P.; Williams, E. A.; Nicodem, D. E.

1975-01-01

Ammonium cyanate is identified as the major product of the photolysis of gaseous NH3-CO mixtures at 206.2 or 184.9 nm. Lesser amounts of urea, biurea, biuret semicarbazide, formamide and cyanide are observed. A series of 18 reactions underlying the formation of photolysis products is presented and discussed. Photocatalytic syntheses of C-14-urea, -formamide, and -formaldehyde are carried out through irradiation of (C-14)O and NH3 in the presence of Vycor, silica gel, or volcanic ash shale surfaces. The possible contributions of the relevant reactions to the abiotic synthesis of organic nitrogen compounds on Mars, the primitive earth, and in interstellar space are examined.

Organotrichlorogermane synthesis by the reaction of elemental germanium, tetrachlorogermane and organic chloride via dichlorogermylene intermediate.

PubMed

Okamoto, Masaki; Asano, Takuya; Suzuki, Eiichi

2004-08-07

Organotrichlorogermanes were synthesized by the reaction of elemental germanium, tetrachlorogermane and organic chlorides, methyl, propyl, isopropyl and allyl chlorides. Dichlorogermylene formed by the reaction of elemental germanium with tetrachlorogermane was the reaction intermediate, which was inserted into the carbon-chlorine bond of the organic chloride to give organotrichlorogermane. When isopropyl or allyl chloride was used as an organic chloride, organotrichlorogermane was formed also in the absence of tetrachlorogermane. These chlorides were converted to hydrogen chloride, which subsequently reacted with elemental germanium to give the dichlorogermylene intermediate. The reaction of elemental germanium, tetrachlorogermane and organic chlorides provides a simple and easy method for synthesizing organotrichlorogermanes, and all the raw materials are easily available.

Synthesis, Morphological and Electrical Characterization of Solution Processable Low Bandgap Organic Materials

DTIC Science & Technology

2008-12-05

bandgap: 1.98 eV Okamoto, Toshihiro; Senatore, Michelle L.; Ling, Mang-Mang; Mallik , Abhijit B.; Tang, Ming L.; Bao, Zhenan. Synthesis...grant: 1. R.A.B. Devine, M.M. Ling, A. Mallik , M.Roberts, Z. Bao, "X-irradiation Effects on Top Contact, Pentacene Based Field Effect Transistors...Semiconductors: Asymmetric Linear Acenes Containing Sulphur ",J. Am. Chem. Soc., 128, 160002-160003,2006. 3. T. Okamoto, M.L. Senatore, M.M. Ling, A.B. Mallik

The effect of oxygen partial pressure on protein synthesis and collagen hydroxylation by mature periodontal tissues maintained in organ cultures

PubMed Central

Yen, Edwin H. K.; Sodek, Jaro; Melcher, Antony H.

1979-01-01

Mature periodontal tissues from adult-mouse first mandibular molars were cultured in a continuous-flow organ-culture system which allowed the regulation of both ascorbic acid concentration and pO2 (oxygen partial pressure). Protein synthesis was measured by analysing the incorporation of [3H]proline into collagenous and non-collagenous proteins during the last 24h of a 2-day culture. At low pO2 [16.0kPa (approx. 120mmHg)] approx. 60% of protein-incorporated [3H]proline was found in collagenous proteins. However, it was evident that this collagen was considerably underhydroxylated. At high pO2 [56.0kPa (approx. 420mmHg)], both the amount of collagen deposited in the tissues and the degree of hydroxylation were increased considerably. In contrast, no significant effect on non-collagenous protein was observed. Tissues cultured at low pO2 for the first 48h were unable to respond to a subsequent increase in pO2 during the last 24h. Analysis of pepsin-solubilized collagen α-chains labelled with [14C]glycine demonstrated the synthesis of both type-I and type-III collagens by explants cultured for 48h at high pO2. Type-III collagen comprised 20–30% of the radioactivity in α-chains in both the periodontal ligament and the tissues of the alveolar process. The pattern of protein synthesis in the alveolar tissues at high pO2 was similar to that observed in these tissues in vivo. However, in the cultured periodontal ligament the proportions of non-collagenous proteins and type-III collagens were increased in comparison with the tissue in vivo. PMID:454369

The interaction between abiotic photodegradation and microbial decomposition under ultraviolet radiation.

PubMed

Wang, Jing; Liu, Lingli; Wang, Xin; Chen, Yiwei

2015-05-01

Elevated ultraviolet (UV) radiation has been demonstrated to stimulate litter decomposition. Despite years of research, it is still not fully understood whether the acceleration in litter degradation is primarily attributed to abiotic photodegradation or the combined effects of abiotic photodegradation and microbial decomposition. In this study, we used meta-analysis to synthesize photodegradation studies and compared the effects of UV radiation on litter decomposition between abiotic and biotic conditions. We also conducted a microcosm experiment to assess the effects of UV radiation on litter biodegradability and microbial activity. Overall, our meta-analysis found that under abiotic photodegradation, UV radiation reduced the remaining litter mass by 1.44% (95% CI: 0.85% to 2.08%), did not affect the remaining lignin and increased the dissolved organic carbon (DOC) concentration by 14.01% (1.49-23.67%). Under combined abiotic photodegradation and microbial decomposition, UV radiation reduced the remaining litter mass and lignin by 1.60% (0.04-3.58%) and 16.07% (9.27-24.23%), respectively, but did not alter DOC concentration. UV radiation had no significant impact on soil microbial biomass carbon (MBC), but it reduced microbial respiration by 44.91% (2.26-78.62%) and altered the composition of the microbial community. In addition, UV radiation reduced nitrogen (N) immobilization by 19.44% (4.77-37.92%). Our microcosm experiment further indicated that DOC concentration and the amount of respired C in UV-treated litter increased with UV exposure time, suggesting that longer UV exposure resulted in greater biodegradability. Overall, our study suggested that UV exposure could increase litter biodegradability by increasing the microbial accessibility of lignin, as well as the labile carbon supply to microbes. However, the remaining litter mass was not different between the abiotic and biotic conditions, most likely because the positive effect of UV radiation on litter

Abiotic Stress Responses and Microbe-Mediated Mitigation in Plants: The Omics Strategies

PubMed Central

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.

2017-01-01

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

Abiotic Stress Responses and Microbe-Mediated Mitigation in Plants: The Omics Strategies.

PubMed

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

2017-01-01

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.

Synthesis and characterization of [BMIM]bromide using microwave-assisted organic synthesis method and its application for dissolution of palm empty fruit bunch

SciTech Connect

Arianie, Lucy, E-mail: lucy205@yahoo.com; Wahyuningrum, Deana, E-mail: deana@chem.itb.ac.id; Nurrachman, Zeily, E-mail: deana@chem.itb.ac.id

The decrease of cellulose crystallinity index of palm empty fruit bunch is crucial for the next application of cellulose as raw material for various biofuel and its derivatives. The aim of this research is to decrease the cellulose crystallinity index of palm empty fruit bunch using 1-butyl-3-methylimidazoliumbromide or [BMIM] bromide which has been synthesized using Microwave-Assisted Organic Synthesis (MAOS) method. Conventional reaction method has also been carried out to synthesize [BMIM]bromide for comparison as well. The characterization of synthesized product using FTIR, {sup 1}H-NMR, {sup 13}C-NMR and LC-MS showed that these reactions have been carried out successfully. The results showedmore » that MAOS method is up to 90% faster in producing [BMIM]bromide compare to the conventional method. The application of [BMIM]bromide for dissolution of palm empty fruit bunch showed that cellulose and lignin could be extracted using stirring process for 20 hours. The decrease of cellulose crystallinity index and its morphology changes were identified using FTIR and Scanning Electron Microscope.« less

Synthesis and characterization of [BMIM]bromide using microwave-assisted organic synthesis method and its application for dissolution of palm empty fruit bunch

NASA Astrophysics Data System (ADS)

Arianie, Lucy; Wahyuningrum, Deana; Nurrachman, Zeily; Natalia, Dessy

2014-03-01

The decrease of cellulose crystallinity index of palm empty fruit bunch is crucial for the next application of cellulose as raw material for various biofuel and its derivatives. The aim of this research is to decrease the cellulose crystallinity index of palm empty fruit bunch using 1-butyl-3-methylimidazoliumbromide or [BMIM] bromide which has been synthesized using Microwave-Assisted Organic Synthesis (MAOS) method. Conventional reaction method has also been carried out to synthesize [BMIM]bromide for comparison as well. The characterization of synthesized product using FTIR, 1H-NMR, 13C-NMR and LC-MS showed that these reactions have been carried out successfully. The results showed that MAOS method is up to 90% faster in producing [BMIM]bromide compare to the conventional method. The application of [BMIM]bromide for dissolution of palm empty fruit bunch showed that cellulose and lignin could be extracted using stirring process for 20 hours. The decrease of cellulose crystallinity index and its morphology changes were identified using FTIR and Scanning Electron Microscope.

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

PubMed

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

2017-07-01

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.

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

ERIC Educational Resources Information Center

Pappenfus, Ted M.; Schliep, Karl B.; Dissanayake, Anudaththa; Ludden, Trevor; Nieto-Ortega, Belen; Lopez Navarrete, Juan T.; Ruiz Delgado, M. Carmen; Casado, Juan

2012-01-01

A series of experiments for undergraduate courses (e.g., organic, physical) have been developed in the area of small molecule organic materials. These experiments focus on understanding the electronic and redox properties of a donor-acceptor molecule that is prepared in a convenient one-step microscale reaction. The resulting intensely colored…

Aquatic organism passage at road-stream crossings—synthesis and guidelines for effectiveness monitoring

Treesearch

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

2012-01-01

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. 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...

Synthesis, Processing, and Characterization of Inorganic-Organic Hybrid Cross-Linked Silica, Organic Polyimide, and Inorganic Aluminosilicate Aerogels

NASA Technical Reports Server (NTRS)

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

2014-01-01

As aerospace applications become ever more demanding, novel insulation materials with lower thermal conductivity, lighter weight and higher use temperature are required to fit the aerospace application needs. Having nanopores and high porosity, aerogels are superior thermal insulators, among other things. The use of silica aerogels in general is quite restricted due to their inherent fragility, hygroscopic nature, and poor mechanical properties, especially in extereme aerospace environments. Our research goal is to develop aerogels with better mechanical and environmental stability for a variety of aeronautic and space applications including space suit insulation for planetary surface missions, insulation for inflatable structures for habitats, inflatable aerodynamic decelerators for entry, descent and landing (EDL) operations, and cryotank insulation for advance space propulsion systems. Different type of aerogels including organic-inorganic polymer reinforced (hybrid) silica-based aerogels, polyimide aerogels and inorganic aluminosilicate aerogels have been developed and examined.

Microwave-assisted synthesis of iron oxide nanoparticles in biocompatible organic environment

NASA Astrophysics Data System (ADS)

Aivazoglou, E.; Metaxa, E.; Hristoforou, E.

2018-04-01

The development of magnetite and maghemite particles in uniform nanometer size has triggered the interest of the research community due to their many interesting properties leading to a wide range of applications, such as catalysis, nanomedicine-nanobiology and other engineering applications. In this study, a simple, time-saving and low energy-consuming, microwave-assisted synthesis of iron oxide nanoparticles, is presented. The nanoparticles were prepared by microwave-assisted synthesis using polyethylene glycol (PEG) or PEG and β-cyclodextrin (β-CD)/water solutions of chloride salts of iron in the presence of ammonia solution. The prepared nano-powders were characterized using X-Ray Diffraction (XRD), Transition Electron Microscopy (TEM), Fourier-transform Infrared Spectroscopy (FTIR), Raman Spectroscopy, Vibrating Sample Magnetometer (VSM), X-Ray Photoelectron Spectroscopy (XPS) and Thermal analysis (TG/DSC). The produced nanoparticles are crystallized mostly in the magnetite and maghemite lattice exhibiting very similar shape and size, with indications of partial PEG coating. Heating time, microwave power and presence of PEG, are the key factors shaping the size properties of nanoparticles. The average size of particles ranges from 10.3 to 19.2 nm. The nanoparticles exhibit a faceted morphology, with zero contamination levels. The magnetic measurements indicate that the powders are soft magnetic materials with negligible coercivity and remanence, illustrating super-paramagnetic behavior.

Diffusion Control in the in Situ Synthesis of Iconic Metal-Organic Frameworks within an Ionic Polymer Matrix.

PubMed

Lim, Jungho; Lee, Eun Ji; Choi, Jae Sun; Jeong, Nak Cheon

2018-01-31

Ionic polymers that possess ion-exchangeable sites have been shown to be a greatly useful platform to fabricate mixed matrices (MMs) where metal-organic frameworks (MOFs) can be in situ synthesized, although the in situ synthesis of MOF has been rarely studied. In this study, alginate (ALG), an anionic green polymer that possesses metal-ion-exchangeable sites, is employed as a platform of MMs for the in situ synthesis of iconic MOFs, HKUST-1, and MOF-74(Zn). We demonstrate for the first time that the sequential order of supplying MOF ingredients (metal ion and deprotonated ligand) into the alginate matrix leads to substantially different results because of a difference in the diffusion of the MOF components. For the examples examined, whereas the infusion of BTC 3- ligand into Cu 2+ -exchanged ALG engendered the eggshell-shaped HKUST-1 layers on the surface of MM spheres, the infusion of Cu 2+ ions into BTC 3- -included alginate engendered the high dispersivity and junction contact of HKUST-1 crystals in the alginate matrix. This fundamental property has been exploited to fabricate a flexible MOF-containing mixed matrix membrane by coincorporating poly(vinyl alcohol). Using two molecular dyes, namely, methylene blue and rhodamine 6G, further, we show that this in situ strategy is suitable for fabricating an MOF-MM that exhibits size-selective molecular uptake.

Synthesis and Electrospraying of Nanoscale MOF (Metal Organic Framework) for High-Performance CO2 Adsorption Membrane

NASA Astrophysics Data System (ADS)

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

2017-01-01

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 CO2 and capacity of adsorbing with 4000-5000 ppm difference from a mixed gas flow of 1% CO2 and 99% N2. 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 CO2 adsorption at room temperature was built with non-dispersive Infrared (NDIR) CO2 sensors. Comparative tests were performed on the membrane to investigate its enhanced adsorption capacity. Three layers of the as-produced membranes displayed CO2 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.

Synthesis and Electrospraying of Nanoscale MOF (Metal Organic Framework) for High-Performance CO2 Adsorption Membrane.

PubMed

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

2017-12-01

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.

Strategies for Distinguishing Abiotic Chemistry from Martian Biochemistry in Samples Returned from Mars

NASA Technical Reports Server (NTRS)

Glavin, D. P.; Burton, A. S.; Callahan, M. P.; Elsila, J. E.; Stern, J. C.; Dworkin, J. P.

2012-01-01

A key goal in the search for evidence of extinct or extant life on Mars will be the identification of chemical biosignatures including complex organic molecules common to all life on Earth. These include amino acids, the monomer building blocks of proteins and enzymes, and nucleobases, which serve as the structural basis of information storage in DNA and RNA. However, many of these organic compounds can also be formed abiotically as demonstrated by their prevalence in carbonaceous meteorites [1]. Therefore, an important challenge in the search for evidence of life on Mars will be distinguishing between abiotic chemistry of either meteoritic or martian origin from any chemical biosignatures from an extinct or extant martian biota. Although current robotic missions to Mars, including the 2011 Mars Science Laboratory (MSL) and the planned 2018 ExoMars rovers, will have the analytical capability needed to identify these key classes of organic molecules if present [2,3], return of a diverse suite of martian samples to Earth would allow for much more intensive laboratory studies using a broad array of extraction protocols and state-of-theart analytical techniques for bulk and spatially resolved characterization, molecular detection, and isotopic and enantiomeric compositions that may be required for unambiguous confirmation of martian life. Here we will describe current state-of-the-art laboratory analytical techniques that have been used to characterize the abundance and distribution of amino acids and nucleobases in meteorites, Apollo samples, and comet- exposed materials returned by the Stardust mission with an emphasis on their molecular characteristics that can be used to distinguish abiotic chemistry from biochemistry as we know it. The study of organic compounds in carbonaceous meteorites is highly relevant to Mars sample return analysis, since exogenous organic matter should have accumulated in the martian regolith over the last several billion years and the

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

NASA Astrophysics Data System (ADS)

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

2013-08-01

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 determining the evolution of the Earth system. Therefore, recent developments in the quantitative modeling of organic matter degradation in marine sediments are critically reviewed. The first part of the review synthesizes the main chemical, biological and physical factors that control organic matter degradation in sediments while the second part provides a general review of the mathematical formulations used to model these processes and the third part evaluates their application over different spatial and temporal scales. Key transport mechanisms in sedimentary environments are summarized and the mathematical formulation of the organic matter degradation rate law is described in detail. The roles of enzyme kinetics, bioenergetics, temperature and biomass growth in particular are highlighted. Alternative model approaches that quantify the degradation rate constant are also critically compared. In the third part of the review, the capability of different model approaches to extrapolate organic matter degradation rates over a broad range of temporal and spatial scales is assessed. In addition, the structure, functions and parameterization of more than 250 published models of organic matter degradation in marine sediments are analyzed. The large range of published model parameters illustrates the complex nature of organic matter dynamics, and, thus, the limited transferability of these parameters from one site to another. Compiled model parameters do not reveal a statistically significant correlation with single environmental characteristics such as water depth, deposition rate or organic matter flux. The lack of a generic framework that allows for model parameters to be

One-pot synthesis of MWW zeolite nanosheets using a rationally designed organic structure-directing agent

DOE PAGES

Luo, Helen Y.; Michaelis, Vladimir K.; Hodges, Sydney; ...

2015-07-22

A new material MIT-1 comprised of delaminated MWW zeolite nanosheets is synthesized in one-pot using a rationally designed organic structure-directing agent (OSDA). The OSDA is comprised of a hydrophilic head segment that resembles the OSDA used to synthesize the zeolite precursor MCM22(P), a hydrophobic tail segment that resembles the swelling agent used to swell MCM22(P), and a di-quaternary ammonium linker that connects both segments. MIT-1 features high crystallinity and surface areas exceeding 500 m 2g -1, and can be synthesized over a wide synthesis window that includes Si/Al ratios ranging from 13 to 67. Characterization data reveal high mesoporosity andmore » acid strength with no detectable amorphous silica phases. In conclusion, compared to MCM-22 and MCM-56, MIT-1 shows a three-fold increase in catalytic activity for the Friedel-Crafts alkylation of benzene with benzyl alcohol.« less

Versatile NiO/mesoporous carbon nanodisks: controlled synthesis from hexagon shaped heterobimetallic metal-organic frameworks.

PubMed

Zeng, Dehong; Yang, Ying; Yang, Feng; Guo, Fangmin; Yang, Senjie; Liu, Baijun; Hao, Shijie; Ren, Yang

2017-08-24

Hexagonal NiO/mesoporous carbon nanodisks (NiO/MCN) are facilely and controllably synthesized via constructing nickel-zinc trimesic acid heterobimetallic metal-organic framework (HMOF) disks before pyrolysis at 910 °C. Tailoring the Ni/(Zn + Ni) feed ratio and the reaction time during the HMOF synthesis creates a well-defined hexagonal carbon nanodisk with properly populated NiO nanocrystals while maintaining high porosity and conductivity. Such an elaborately fabricated NiO/MCN is highly stable, and exhibits the largest specific capacitance of 261 F g -1 and the highest specific activity factor of 1.93 s -1 g -1 of any composite nanodisk during the capacitive test and 4-nitrophenol reduction, respectively.

Template synthesis of hollow MoS2-carbon nanocomposites using microporous organic polymers and their lithium storage properties.

PubMed

Jin, Jaewon; Kim, Bolyong; Kim, Mincheol; Park, Nojin; Kang, Sungah; Lee, Sang Moon; Kim, Hae Jin; Son, Seung Uk

2015-07-14

This work shows that hollow and microporous organic polymers (H-MOPs) are good templating materials for the synthesis of inorganic material-carbon nanocomposites. The precursor compound, (NH4)2MoS4, was incorporated into H-MOPs. Heat treatment under argon resulted in the formation of hollow MoS2-carbon nanocomposites (MSC). According to microscopic analysis, the MoS2 in the MSC has a layered structure with an elongated interlayer distance. The MSC showed high reversible discharge capacities up to 802 mA h g(-1) after 30 cycles and excellent rate performance for lithium ion batteries. The promising electrochemical performance of the MSC is attributed to the very thin and disordered nature of MoS2 in the carbon skeleton. The role of chemical components of the MSC in the electrochemical process was suggested.

Synthesis of five- and six-membered cyclic organic peroxides: Key transformations into peroxide ring-retaining products

PubMed Central

Borisov, Dmitry A; Vil’, Vera A; Dembitsky, Valery M

2014-01-01

Summary The present review describes the current status of synthetic five and six-membered cyclic peroxides such as 1,2-dioxolanes, 1,2,4-trioxolanes (ozonides), 1,2-dioxanes, 1,2-dioxenes, 1,2,4-trioxanes, and 1,2,4,5-tetraoxanes. The literature from 2000 onwards is surveyed to provide an update on synthesis of cyclic peroxides. The indicated period of time is, on the whole, characterized by the development of new efficient and scale-up methods for the preparation of these cyclic compounds. It was shown that cyclic peroxides remain unchanged throughout the course of a wide range of fundamental organic reactions. Due to these properties, the molecular structures can be greatly modified to give peroxide ring-retaining products. The chemistry of cyclic peroxides has attracted considerable attention, because these compounds are used in medicine for the design of antimalarial, antihelminthic, and antitumor agents. PMID:24454562

Synthesis and characterization of a helicene-based imidazolium salt and its application in organic molecular electronics.

PubMed

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

2015-02-02

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.

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

PubMed

Knall, Astrid-Caroline; Jones, Andrew O F; Kunert, Birgit; Resel, Roland; Reishofer, David; Zach, Peter W; Kirkus, Mindaugas; McCulloch, Iain; Rath, Thomas

2017-01-01

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 PC 70 BM, 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 CuInS 2 nanocrystals as inorganic phase, which were prepared from precursors directly in the polymer matrix without using additional capping ligands. The PPD-BDT/CuInS 2 hybrid solar cells showed comparably high photovoltages and a power conversion efficiency of 2.2%.

Synthesis and characterization of a novel organic corrosion inhibitor for mild steel in 1 M hydrochloric acid

NASA Astrophysics Data System (ADS)

Ahmed, Mohammed H. Othman; Al-Amiery, Ahmed A.; Al-Majedy, Yasmin K.; Kadhum, Abdul Amir H.; Mohamad, Abu Bakar; Gaaz, Tayser Sumer

2018-03-01

The synthesis and characterization of a novel organic corrosion inhibitor (4-(3-mercapto-5,6,7,8-tetrahydro-[1,2,4]triazolo[4,3-b][1,2,4,5]tetrazin-6-yl)phenol), for mild steel in 1 M hydrochloric acid (HCl) has been successfully reported for the first time. The inhibitor evaluated as corrosion inhibitor for mild steel in 1 M of Hydrochloric acid solution using electrochemical impedance spectroscopy (EIS), and electrochemical frequency modulation (EFM) measurement techniques. Changes in the impedance parameters suggested an adsorption of the inhibitor onto the mild steel surface, leading to the formation of protective films. The results show that the inhibition efficiencies increased with increasing the concentrations of the inhibitors and decreased with increasing temperature. The maximum inhibition efficiency up to 67% at the maximum concentration 0.5 mM. This shows that those inhibitors are effective in helping to reduce and slowing down the corrosion process that occurs to mild steel with a hydrochloric acid solution by providing an organic inhibitor for the mild steel that can be weakened by increasing the temperature. The adsorption process of the synthesized organic inhibitor depends on its electronic characteristics in addition to steric effects and the nature of metal surface, temperature degree and the varying degrees of surface-site activity. The synthesized inhibitor molecules were absorbed by metal surface and follow Langmuir isotherms.

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

PubMed

Pontrello, Jason K

2015-01-01

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.

Italian chemists' contributions to named reactions in organic synthesis: an historical perspective.

PubMed

Papeo, Gianluca; Pulici, Maurizio

2013-09-04

From the second half of the 19th century up to modern times, the tremendous contribution of Italian chemists to the development of science resulted in the discovery of a number of innovative chemical transformations. These reactions were subsequently christened according to their inventors' name and so entered into the organic chemistry portfolio of "named organic reactions". As these discoveries were being conceived, massive social, political and geographical changes in these chemists' homeland were also occurring. In this review, a brief survey of known (and some lesser known) named organic reactions discovered by Italian chemists, along with their historical contextualization, is presented.

MICROSCALE METABOLIC, REDOX AND ABIOTIC REACTIONS IN HANFORD 300 AREA SUBSURFACE SEDIMENTS

SciTech Connect

Beyenal, Haluk; McLEan, Jeff; Majors, Paul

2013-11-14

The Hanford 300 Area is a unique site due to periodic hydrologic influence of river water resulting in changes in groundwater elevation and flow direction. This area is also highly subject to uranium remobilization, the source of which is currently believed to be the region at the base of the vadose zone that is subject to period saturation due to the changes in the water levels in the Columbia River. We found that microbial processes and redox and abiotic reactions which operate at the microscale were critical to understanding factors controlling the macroscopic fate and transport of contaminants in themore » 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.« less

A Synthesis of "o"-Chlorocinnamic Acid Utilizing a Meerwein Reaction: An Undergraduate Organic Experiment.

ERIC Educational Resources Information Center

Cleland, George H.

1978-01-01

The Meerwein reaction is often omitted from undergraduate organic chemistry laboratory books. This experiment, the preparation of "o"-chlorocinnamic acid from "o"-chloroanaline, illustrates this section. (BB)

A modular microfluidic platform for the synthesis of biopolymeric nanoparticles entrapping organic actives

NASA Astrophysics Data System (ADS)

Chronopoulou, Laura; Sparago, Carolina; Palocci, Cleofe

2014-11-01

Using a novel and versatile capillary microfluidic flow-focusing device we fabricated monodisperse drug-loaded nanoparticles from biodegradable polymers. A model amphiphilic drug (dexamethasone) was incorporated within the biodegradable matrix of the particles. The influence of flow rate ratio, polymer concentration, and microreactor-focusing channel dimensions on nanoparticles' size and drug loading has been investigated. The microfluidic approach resulted in the production of colloidal polymeric nanoparticles with a narrow size distribution (diameters ranging between 35 and 350 nm) and useful morphological characteristics. This technique allows the fast, low cost, easy, and automated synthesis of polymeric nanoparticles, therefore it may become a useful approach in the progression from laboratory scale to pilot-line scale processes.

Digitization of multistep organic synthesis in reactionware for on-demand pharmaceuticals.

PubMed

Kitson, Philip J; Marie, Guillaume; Francoia, Jean-Patrick; Zalesskiy, Sergey S; Sigerson, Ralph C; Mathieson, Jennifer S; Cronin, Leroy

2018-01-19

Chemical manufacturing is often done at large facilities that require a sizable capital investment and then produce key compounds for a finite period. We present an approach to the manufacturing of fine chemicals and pharmaceuticals in a self-contained plastic reactionware device. The device was designed and constructed by using a chemical to computer-automated design (ChemCAD) approach that enables the translation of traditional bench-scale synthesis into a platform-independent digital code. This in turn guides production of a three-dimensional printed device that encloses the entire synthetic route internally via simple operations. We demonstrate the approach for the γ-aminobutyric acid receptor agonist, (±)-baclofen, establishing a concept that paves the way for the local manufacture of drugs outside of specialist facilities. Copyright © 2018 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works.

Before the Ring: synthesis of linear organic molecules in astrophysical ices by low energy electron impact

NASA Astrophysics Data System (ADS)

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 (<60 eV) electrons. For example, for CD4 ices we observe the formation and desorption of energetic ions such as D3 + , CD5 + , and C2 Dn + (n = 2-5), as well as three carbon containing chains, that are also observed to desorb from C2 D2 films; for oxygen rich methane ices we observe the synthesis and desorption of H2 O+ , H3 O+ , as well as formaldehyde type cations, viz., Hn CO+ (n = 1-3), among others. The formation of all these linear, pre-biotic molecular species, produced here by electron initiated

Combinatorial synthesis by nature: volatile organic sulfur-containing constituents of Ruta chalepensis L.

PubMed

Escher, Sina; Niclass, Yvan; van de Waal, Matthijs; Starkenmann, Christian

2006-09-01

Ongoing interest in discovering new natural fragrance and flavor ingredients prompted us to examine a solvent extract of sulfurous-sweaty smelling Ruta chalepensis L. (Rutaceae) plant material more closely. Twenty-one sulfur-containing constituents of similar structures were identified by GC/MS techniques. Amongst them, 14 have never been described to occur in nature. The compounds 1-18 belong to a family of natural flavor and fragrance molecules having a 1,3-positioned O,S moiety in common. The identities of the natural constituents were confirmed by comparison with synthetic reference samples, and the organoleptic properties of the latter were studied. The relative and absolute configurations of the four stereoisomers of 4-methyl-3-sulfanylhexan-1-ol (5) were established by stereoselective synthesis. The natural isomers consisted of a 65 : 35 mixture of (3R,4S)-5 and (3S,4S)-5.

Homolytic substitution at phosphorus for C–P bond formation in organic synthesis

PubMed Central

2013-01-01

Summary Organophosphorus compounds are important in organic chemistry. This review article covers emerging, powerful synthetic approaches to organophosphorus compounds by homolytic substitution at phosphorus with a carbon-centered radical. Phosphination reagents include diphosphines, chalcogenophosphines and stannylphosphines, which bear a weak P–heteroatom bond for homolysis. This article deals with two transformations, radical phosphination by addition across unsaturated C–C bonds and substitution of organic halides. PMID:23843922

Coordinated Actions of Glyoxalase and Antioxidant Defense Systems in Conferring Abiotic Stress Tolerance in Plants

PubMed Central

Hasanuzzaman, Mirza; Nahar, Kamrun; Hossain, Md. Shahadat; Mahmud, Jubayer Al; Rahman, Anisur; Inafuku, Masashi; Oku, Hirosuke; Fujita, Masayuki

2017-01-01

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

Polyamines and abiotic stress in plants: a complex relationship1

PubMed Central

Minocha, Rakesh; Majumdar, Rajtilak; Minocha, Subhash C.

2014-01-01

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 protectors from as well as perpetrators 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. PMID:24847338

Multicapillary Flow Reactor: Synthesis of 1,2,5-Thiadiazepane 1,1-Dioxide Library Utilizing One-Pot Elimination and Inter-/Intramolecular Double aza-Michael Addition Via Microwave-Assisted, Continuous-Flow Organic Synthesis (MACOS)

PubMed Central

Ullah, Farman; Zang, Qin; Javed, Salim; Zhou, Aihua; Knudtson, Christopher A.; Bi, Danse; Hanson, Paul R.; Organ, Michael G.

2013-01-01

A microwave-assisted, continuous-flow organic synthesis (MACOS) protocol for the synthesis of functionalized 1,2,5-thiadiazepane 1,1-dioxide library, utilizing a one-pot elimination and inter-/intramolecular double aza-Michael addition strategy is reported. The optimized protocol in MACOS was utilized for scale-out and further extended for library production using a multicapillary flow reactor. A 50-member library of 1,2,5-thiadiazepane 1,1-dioxides was prepared on a 100- to 300-mg scale with overall yields between 50 and 80% and over 90 % purity determined by proton nuclear magnetic resonance (1H-NMR) spectroscopy. PMID:24244871

The Promoter of AtUSP Is Co-regulated by Phytohormones and Abiotic Stresses in Arabidopsis thaliana.

PubMed

Bhuria, Monika; Goel, Parul; Kumar, Sanjay; Singh, Anil K

2016-01-01

Universal stress proteins (USPs) are known to be expressed in response to various abiotic stresses in a wide variety of organisms, such as bacteria, archaebacteria, protists, algae, fungi, plants, and animals. However, in plants, biological function of most of the USPs still remains obscure. In the present study, Arabidopsis USP gene ( AtUSP ) showed induction in response to abscisic acid (ABA) and various abiotic stresses viz . heat, dehydration, salt, osmotic, and cold stresses. Additionally, in silico analysis of AtUSP promoter identified several cis -elements responsive to phytohormones and abiotic stresses such as ABRE, ERE, DRE, and HSE, etc. To functionally validate the AtUSP promoter, the 1115 bp region of promoter was characterized under phytohormone and abiotic stress treatments. Deletion analysis of promoter was carried out by cloning the full length promoter (D0) and its three 5' deletion derivatives, D1 (964 bp), D2 (660 bp), and D3 (503 bp) upstream of the β-glucuronidase (GUS) reporter gene, which were then stably transformed in Arabidopsis plants. The AtUSP promoter (D0) showed minimal activity under non-stress conditions which was enhanced in response to phytohormone treatments (ABA and ACC) and abiotic stresses such as dehydration, heat, cold, salt, and osmotic stresses. The seedlings harboring D1 and D2 deletion fragments showed constitutive GUS expression even under control condition with increased activity almost under all the treatments. However, D3 seedlings exhibited complete loss of activity under control condition with induction under ACC treatment, dehydration, heat, oxidative, salt, and osmotic stresses. Thus, present study clearly showed that AtUSP promoter is highly inducible by phytohormones and multiple abiotic stresses and it can be exploited as stress inducible promoter to generate multi-stress tolerant crops with minimal effects on their other important traits.

Aquatic organism passage at road-stream crossings—synthesis and guidelines for effectiveness monitoring

USGS Publications Warehouse

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

2012-01-01

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

Synthesis of organosilicon derivatives of [1]benzothieno[3,2-b][1]-benzothiophene for efficient monolayer Langmuir-Blodgett organic field effect transistors.

PubMed

Borshchev, O V; Sizov, A S; Agina, E V; Bessonov, A A; Ponomarenko, S A

2017-01-16

For the first time, the synthesis of organosilicon derivatives of dialkyl[1]benzothieno[3,2-b][1]-benzothiophene (BTBT) capable of forming a semiconducting monolayer at the water-air interface is reported. Self-assembled monolayer organic field-effect transistors prepared from these materials using the Langmuir-Blodgett technique showed high hole mobilities and excellent air stability.

Continuing Education and Training and the Labour Market. Synthesis Report on a Conference Organized by CEDEFOP (Berlin, West Germany, March 8-9, 1984).

ERIC Educational Resources Information Center

Hege, Adelheid

This synthesis report summarizes a conference organized to examine the current situation regarding the continuing education and training of adults in the European Community and to formulate proposals for action. Some 60 conference participants examined various research reports, conducted discussions, and presented papers on three major topics:…

Synthesis, Characterization, and Secondary Structure Determination of a Silk-Inspired, Self-Assembling Peptide: A Laboratory Exercise for Organic and Biochemistry Courses

ERIC Educational Resources Information Center

Albin, Tyler J.; Fry, Melany M.; Murphy, Amanda R.

2014-01-01

This laboratory experiment gives upper-division organic or biochemistry undergraduate students a comprehensive look at the synthesis, chemical characterization, self-assembly, and secondary structure determination of small, N-acylated peptides inspired by the protein structure of silkworm silk. All experiments can be completed in one 4 h lab…

The Synthesis and Isolation of N-Tert-Butyl-2-Phenylsuccinamic Acid and N-Tert-Butyl-3-Phenylsuccinamic Acid: An Undergraduate Organic Chemistry Laboratory Experiment

ERIC Educational Resources Information Center

Cesare, Victor; Sadarangani, Ishwar; Rollins, Janet; Costello, Dennis

2004-01-01

The facile, high yielding synthesis of phenylsuccinamic acids is described and one of these syntheses, the reaction of phenylsuccinic anhydride with tert-butylamine, is successfully modified and adapted for use in the second-semester organic chemistry laboratory at St. John's University. Succinamic acids are compounds that contain both the amide…

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

PubMed

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

2017-09-12

This study reports on the design and synthesis of an unsymmetrical π-conjugated organic molecule composed of perylene diimide, thienyl diketopyrrolopyrrole, and indoloquinoxaline pieced together using direct heteroarylation. This material demonstrates unprecedented response in the thin-film upon post-deposition solvent vapor annealing, resulting in dramatic red-shifts in optical absorption. Such changes were utilized to enhance photocurrent generation in P3HT based organic solar cells.

Enzymatic synthesis of esculin ester in ionic liquids buffered with organic solvents.

PubMed

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

2009-05-13

The enzymatic esterification of esculin catalyzed by Candida antarctica lipase B (Novozym 435) was carried out in ionic liquid (IL)-organic solvent mixed systems in comparison with individual systems. The reaction behaviors in IL-organic solvents were systemically evaluated using acetone as a model solvent. With organic solvents as media, the esterification rates of esculin depended mainly on its solubility in solvents; for the reactions in ILs, the reaction rates were generally low, and the anion part of the IL played a critical role in enzyme activity. Therefore, the esterification of esculin 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 [Tf(2)N](-) > [PF(6)](-) > [BF(4)](-) > [CF(3)SO(3)](-) > [C(4)F(9)SO(3)](-) > [TAF](-) > [MDEGSO(4)](-) > [OctSO(4)](-) > [ES](-) = [DMP](-) = [OTs](- )= Cl(-). The reaction behaviors differed in different systems and largely depended on the properties of the ILs and organic solvents. In general, improvements were observed in terms of both solubility and reaction efficiency. The knowledge acquired in this work gives a better understanding of multiple interactions in IL-organic solvent systems, which provide guidance for system design and optimization.

Microwave: An Important and Efficient Tool for the Synthesis of Biological Potent Organic Compounds.

PubMed

Kumari, Kamlesh; Vishvakarma, Vijay K; Singh, Prashant; Patel, Rajan; Chandra, Ramesh

2017-01-01

Green Chemistry is an interdisciplinary science or it can also be explained as a branch of chemistry. It is generally described as the chemistry to aim to synthesize chemical compounds to trim down the utilization of harmful chemicals proposed by the Environmental Protection Agency (EPA). Recently, the plan of academicians, researchers, industrialists is to generate greener and more efficient methodologies to carry out various organic syntheses. In the present scenario, green chemistry utilizes the raw materials economically, minimizes the waste and prevents the uses of harmful or hazardous chemicals to make the organic reactions simple and efficient. Microwave technique is a new, simple and efficient technology which opens new prospects to the chemists to carry out various organic and inorganic reactions, which are difficult via conventional methodology. It is used to decrease the duration of time to carry various organic transformation along with maximum yield, minimum by-products, minimum energy utilization, less manpower etc. e.g. various famous organic reactions have been carried out by various research groups like Aldol condensation, Knoevenagel condensation, Beckmann rearrangement, Vilsmeier reaction, Perkin reaction, Benzil-Benzilic acid rearrangement, Fischer cyclization, Mannich reaction, Claisen-Schmidt condensation, etc. Further, reduction, oxidation, coupling, condensation reaction were also performed using microwave technology. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

Contributions of Fe Minerals to Abiotic Dechlorination

EPA Science Inventory

Most applications of enhanced in situ bioremediation are based on biological reductive dechlorination. Anaerobic metabolism can also produce reactive minerals that allow for in situ biogeochemical transformation of chlorinated organic contaminants such as PCE, TCE, and cis-DCE. ...

Organic synthesis via irradiation and warming of ice grains in the solar nebula.

PubMed

Ciesla, Fred J; Sandford, Scott A

2012-04-27

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.

Organic Synthesis via Irradiation and Warming of Ice Grains in the Solar Nebula

NASA Technical Reports Server (NTRS)

Ciesla, Fred J.; Sanford, Scott A.

2012-01-01

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.

Organic-inorganic hybrid polymer electrolytes based on polyether diamine, alkoxysilane, and trichlorotriazine: Synthesis, characterization, and electrochemical applications

NASA Astrophysics Data System (ADS)

Saikia, Diganta; Wu, Cheng-Gang; Fang, Jason; Tsai, Li-Duan; Kao, Hsien-Ming

2014-12-01

A new type of highly conductive organic-inorganic hybrid polymer electrolytes has been synthesized by the reaction of poly(propylene glycol)-block-poly(ethylene glycol)-block-poly(propylene glycol) bis(2-aminopropyl ether), 2,4,6-trichloro-1,3,5-triazine and alkoxysilane precursor 3-(glycidyloxypropyl)trimethoxysilane, followed by doping of LiClO4. The 13C and 29Si solid-sate NMR results confirm the successful synthesis of the organic-inorganic hybrid structure. The solid hybrid electrolyte thus obtained exhibits a maximum ionic conductivity of 1.6 × 10-4 S cm-1 at 30 °C, which is the highest among the organic-inorganic hybrid electrolytes. The hybrid electrolytes are electrochemically stable up to 4.2 V. The prototype electrochromic device with such a solid hybrid electrolyte demonstrates a good coloration efficiency value of 183 cm2 C-1 with a cycle life over 200 cycles. For the lithium-ion battery test, the salt free solid hybrid membrane is swelled with a LiPF6-containing electrolyte solution to reach an acceptable ionic conductivity value of 6.5 × 10-3 S cm-1 at 30 °C. The battery cell carries an initial discharge capacity of 100 mAh g-1 at 0.2C-rate and a coulombic efficiency of about 95% up to 30 cycles without the sign of cell failure. The present organic-inorganic hybrid electrolytes hold promise for applications in electrochromic devices and lithium ion batteries.

Total Observed Organic Carbon (TOOC): A Synthesis of North American Observations

NASA Technical Reports Server (NTRS)

Heald, C. L.; Goldstein, A. H.; Allan, J. D.; Aiken, A. C.; Apel, E.; Atlas, E. L.; Baker, A. K.; Bates, T. S.; Beyersdorf, A. J.; Blake, D. R.;

Synthesis and characterization of axial heterojunction inorganic-organic semiconductor nanowire arrays.

PubMed

Chen, Nan; Qian, Xuemin; Lin, Haowei; Liu, Huibiao; Li, Yongjun; Li, Yuliang

2011-11-07

The end-to-end P-N heterojunction nanowire arrays combined organic (poly[1,4-bis(pyrrol-2-yl)benzene], BPB) and inorganic (CdS) molecules have been successfully designed and fabricated. The electrical properties of P-N heterojunctions of organic-inorganic nanowire arrays were investigated. The diode nature and rectifying feature of P-N heterojunction nanowire arrays were observed. The rectification ratio of the diode increased from 29.9 to 129.7 as the illumination intensity increased. The material exhibits a new property, which is an improvement in the integration of the physical and chemical properties of the two independent components.

Ferrocenyl and organic novobiocin derivatives: Synthesis and their in vitro biological activity.

PubMed

Mbaba, Mziyanda; Mabhula, Amanda N; Boel, Natasha; Edkins, Adrienne L; Isaacs, Michelle; Hoppe, Heinrich C; Khanye, Setshaba D

2017-07-01

A focused series of novobiocin derivatives containing a ferrocene unit together with their corresponding organic novobiocin analogues have been synthesized in modest to good yields. These compounds were screened for biological activity against a chloroquine-sensitive strain of Plasmodium falciparum (3D7) and human breast cancer cell line (HCC38). With the exception of compounds 5c and 5d, the general trend observed is that incorporation of the ferrocene moiety into novobiocin scaffold resulted in compounds 6a-d/6f showing enhanced activity compared to organic analogues 5a-b and 5e-f. Copyright © 2017 Elsevier Inc. All rights reserved.

Ion-molecule condensation reactions: a mechanism for organic synthesis in ionized reducing atmospheres.

PubMed

Meot-Ner, M

1978-12-01

The CH3+ ion, formed in ionized methane, undergoes consecutive eliminative condensation reactions with methane to form the carbonium ions C2H5+, i-C3H7+ and t-C4H9+. At T smaller than 500 degrees K, NCH4 greater than 10(16) cm-3 these ions react with NH3 in competitive condensation -- H+ transfer reactions, e.g. C2H5 + NH3 M leads to C2H5NH3+ leads to NH4+ + C2H4 At particle densities of NCH4 smaller than 10(16) cm-3 proton transfer is the only significant reaction channel. At NCH4 greater than 10(17) cm-3 condensation constitutes 5--20% of the overall reactions. The product of the condensation reaction further associates with CO2 to form C2H5NH3+ . CO2; the atomic composition of this cluster ion is identical with the protonated amino acid alanine. The carbonium ions i-C3H7+ and t-C4H9+ condense also with HCN to yield protonated isocyanides. HCNH% also appears to condense with HCN at T greater than 570 degrees K, and form cluster ions with HCN at lower temperatures. The rate constants of the condensation reactions vary with temperature and pressure in a complex manner. Under conditions similar to those on Titan at an altitude of 100 km (T = 100--150 degrees K, NCH4 approximately 10(18) cm-3), with a methane atmosphere containing 1% H2 and traces of NH3 and H2O, ion-molecule condensation reactions followed by H+ transfer are expected to lead to the atmospheric synthesis of C2H6, C3H8, CH3OH, C2H5OH and the terminal ions NH4+, CH3NH3+ and C2H5NH3+. At higher temperatures (250 degrees K smaller than T smaller than 400 degrees K), the synthesis of i-C4H10, i-C3H7OH and t-C4H9OH and of the ions i-C3H7NH3+ and t-C4H9NH3+ is also expected. Electron recombination of the terminal ions may yield amines, imines and nitriles. Cycles of protonation and dissociative recombination of the alkanes and alcohols produced in condensation reactions will also produce unsaturated hydrocarbons, ketones and aldehydes in the ionized atmosphere.

Synthesis of hybrid inorganic/organic nitric oxide-releasing silica nanoparticles for biomedical applications

NASA Astrophysics Data System (ADS)

Carpenter, Alexis Wells

Nitric oxide (NO) is an endogenously produced free radical involved in a number of physiological processes. Thus, much research has focused on developing scaffolds that store and deliver exogenous NO. Herein, the synthesis of N-diazeniumdiolate-modified silica nanoparticles of various physical and chemical properties for biomedical applications is presented. To further develop NO-releasing silica particles for antimicrobial applications, a reverse microemulsion synthesis was designed to achieve nanoparticles of distinct sizes and similar NO release characteristics. Decreasing scaffold size resulted in improved bactericidal activity against Pseudomonas aeruginosa. Confocal microscopy revealed that the improved efficacy resulted from faster particle-bacterium association kinetics. To broaden the therapeutic potential of NO-releasing silica particles, strategies to tune NO release characteristics were evaluated. Initially, surface hydrophobicity and NO release kinetics were tuned by grafting hydrocarbon- and fluorocarbon-based silanes onto the surface of N-diazeniumdiolate-modified particles. The addition of fluorocarbons resulted in a 10x increase in the NO release half-life. The addition of short-chained hydrocarbons to the particle surface increased their stability in hydrophobic electrospun polyurethanes. Although NO release kinetics were longer than that of unmodified particles, durations were still limited to <7 days. An alternative strategy for increasing NO release duration involved directly stabilizing the N-diazeniumdiolate using O2-protecting groups. O2-Methoxymethyl 1-(4-(3-(trimethoxysilyl)propyl))piperazin-1-yl)diazen-1-ium-1,2-diolate (MOM-Pip/NO) was grafted onto mesoporous silica nanoparticles to yield scaffolds with an NO payload of 2.5 μmol NO/mg and an NO release half-life of 23 d. Doping the MOM-Pip/NO-modified particles into resin composites yielded antibacterial NO-releasing dental restorative materials. A 3-log reduction in viable adhered

Abiotic formation of RNA-like oligomers by montmorillonite catalysis: part II

NASA Astrophysics Data System (ADS)

Ertem, Gözen; Snellinger-O'Brien, Ann M.; Ertem, M. C.; Rogoff, D. A.; Dworkin, Jason P.; Johnston, Murray V.; Hazen, Robert M.

2008-01-01

This work is an extension of our previous studies carried out to investigate the possible catalytic role of minerals in the abiotic synthesis of biologically important molecules. In the presence of montmorillonite, a member of the phyllosilicate group minerals that are abundant on Earth and identified on Mars, activated RNA monomers, namely 5‧-phosphorimidazolides of nucleosides (ImpNs), undergo condensation reactions in aqueous electrolyte solution producing oligomers with similar structures to short RNA fragments. Analysis of the linear trimer isomers formed in the reaction of a mixture of activated adenosine and cytidine monomers (ImpA and ImpC, respectively) employing high-performance liquid chromatography, selective enzymatic hydrolysis and matrix-assisted laser desorption/ionization mass spectroscopy molecular weight measurements demonstrate that montmorillonite catalysis facilitates the formation of hetero-isomers containing 56% A- and 44% C-monomer incorporated in their structure. The results also show that 56% of the monomer units are linked together by RNA-like 3‧, 5‧-phosphodiester bonds. These results follow the same trend observed in our most recent work studying the reaction of activated adenosine and uridine monomers, and support Bernal's hypothesis proposing the possible catalytic role of minerals in the abiotic processes in the course of chemical evolution.

Lipase-supported metal-organic framework bioreactor catalyzes warfarin synthesis.

PubMed

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

2015-01-02

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.

Temperature and soil organic matter decomposition rates - synthesis of current knowledge and a way forward

Treesearch

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

2011-01-01

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...

Use of Enzymes in Organic Synthesis: Reduction of Ketones by Baker's Yeast Revisited

ERIC Educational Resources Information Center

Patterson, James; Sigurdsson, Snorri Th.

2005-01-01

The reduction of ethyl acetoacetate using common baker's yeast is a traditional experiment that shows the stereoselective power of a biochemical system. Addition of organic solvents to aqueous reaction system increased the yields and reproducibility of the experiment thus overcoming the two problems associated with the experiment, low yield, and…

Cocrystal Controlled Solid-State Synthesis: A Green Chemistry Experiment for Undergraduate Organic Chemistry

ERIC Educational Resources Information Center

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

2008-01-01

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…

Synthesis and Characterization of Calixarene Tetraethers: An Exercise in Supramolecular Chemistry for the Undergraduate Organic Laboratory

ERIC Educational Resources Information Center

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

2016-01-01

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…

Independent Synthesis Projects in the Organic Chemistry Teaching Laboratories: Bridging the Gap between Student and Researcher

ERIC Educational Resources Information Center

Keller, Valerie A.; Kendall, Beatrice Lin

2017-01-01

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…

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

PubMed

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

2017-09-05

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.

Identification and Characterization Methods for Reactive Minerals Responsible for Natural Attenuation of Chlorinated Organic Compounds in Ground Water

EPA Science Inventory

Over the past decade, there has been a growing awareness of the contribution of abiotic processes to the natural degradation of chlorinated organic contaminants in aquifer material. These abiotic processes contribute to risk management of the contaminants through monitored natur...

Synthesis of Conjugated Small Molecules and Polymers by a Palladium Catalyzed Cyclopentannulation Strategy: Towards New Organic Semiconductors

NASA Astrophysics Data System (ADS)

Bheemireddy, Sambasiva Reddy

The utility of conjugated small molecules and polymers as organic semiconductors have seen a tremendous growth in research and development in academia as well as industry because of their processability and flexibility advantages in comparison to inorganic semiconductors. The extensive research over the years has produced a large number of p-type (hole conducting) and n-type (electron conducting) semiconductors that can be used to construct organic electronic devices. Of these materials, p-type semiconductors are more established and extensively studied because of the ease of preparation as well as their better general stability in comparison to n-type materials. Despite recent research into the development of n-type materials, fullerene (C60 and C 70) and its derivatives are still the predominant materials used as electron acceptors for OPV applications. By taking advantage of the electron accepting behavior of cyclopenta[hi]aceanthrylene fragment of C70, we have designed and synthesized new materials based on cyclopenta-fused polycyclic aromatic hydrocarbons (CP-PAHs). By using a newly developed palladium catalyzed cyclopentannulation methodology, 1,2,6,7- tetraarylcyclopenta[hi]aceanthrylenes were prepared by treating diarylethynylenes with 9,10-dibromoanthracene. Scholl cyclodehydrogenation was used to close the externally fused aryl groups to provide access to contorted 2,7,13,18- tetraalkoxytetrabenzo[f,h,r,t]rubicenes. The contortion provides access to more soluble materials than their planar counterparts but still ii allows significant pi-pi stacking between molecules. Using a modified palladium catalyzed cyclopentannulation polymerization followed by a cyclodehydrogenation reaction, a nonconventional synthesis of CP-PAH embedded ladder polymers was also achieved. These ladder polymers possess broad UV-Vis absorptions and narrow optical gaps of 1.17-1.29 eV. The synthesis of new donor-acceptor copolymers incorporating electron accepting 1,2,6,7- tetra(4

The prebiotic synthesis of oligonucleotides

NASA Technical Reports Server (NTRS)

Oro, J.; Stephen-Sherwood, E.

1974-01-01

This paper is primarily a review of recent developments in the abiotic synthesis of nucleotides, short chain oligonucleotides, and their mode of replication in solution. It also presents preliminary results from this laboratory on the prebiotic synthesis of thymidine oligodeoxynucleotides. A discussion, based on the physicochemical properties of RNA and DNA oligomers, relevant to the molecular evolution of these compounds leads to the tentative hypothesis that oligodeoxyribonucleotides of about 12 units may have been of sufficient length to initiate a self replicating coding system. Two models are suggested to account for the synthesis of high molecular weight oligomers using short chain templates and primers.

Choline acetyltransferase and organic cation transporters are responsible for synthesis and propionate-induced release of acetylcholine in colon epithelium.

PubMed

Bader, Sandra; Klein, Jochen; Diener, Martin

2014-06-15

Acetylcholine is not only a neurotransmitter, but is found in a variety of non-neuronal cells. For example, the enzyme choline acetyltransferase (ChAT), catalyzing acetylcholine synthesis, is expressed by the colonic epithelium of different species. These cells release acetylcholine across the basolateral membrane after luminal exposure to propionate, a short-chain fatty acid. The functional consequence is the induction of chloride secretion, measurable as increase in short-circuit current (Isc) in Ussing chamber experiments. It is unclear how acetylcholine is produced and released by colonic epithelium. Therefore, the aim of the present study was the identification (on mRNA and protein level) and functional characterization (in Ussing chamber experiments combined with HPLC detection of acetylcholine) of transporters/enzymes in the cholinergic system of rat colonic epithelium. Immunohistochemical staining as well as RT-PCR revealed the expression of high-affinity choline transporter, ChAT, carnitine acetyltransferase (CarAT), vesicular acetylcholine transporter (VAChT), and organic cation transporters (OCT 1, 2, 3) in colonic epithelium. In contrast to blockade of ChAT with bromoacetylcholine, inhibition of CarAT with mildronate did not inhibit the propionate-induced increase in Isc, suggesting a predominant synthesis of epithelial acetylcholine by ChAT. Although being expressed, blockade of VAChT with vesamicol was ineffective, whereas inhibition of OCTs with omeprazole and corticosterone inhibited propionate-induced Isc and the release of acetylcholine into the basolateral compartment. In summary, OCTs seem to be involved in regulated acetylcholine release by colonic epithelium, which is assumed to be involved in chemosensing of luminal short-chain fatty acids by the intestinal epithelium. Copyright © 2014 Elsevier B.V. All rights reserved.

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

DOE PAGES

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

2016-06-16

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

Chitosan-microreactor: a versatile approach for heterogeneous organic synthesis in microfluidics.

PubMed

Basavaraju, K C; Sharma, Siddharth; Singh, Ajay K; Im, Do Jin; Kim, Dong-Pyo

2014-07-01

Microreactors have been proven to be efficient tools for a variety of homogeneous organic transformations due to their mixing efficiency, which results in very fast reactions, better heat and mass transfer, and simple scale-up. However, in heterogeneous catalytic reactions each catalyst needs an individual substrate as support. Herein, a versatile approach to immobilize metal catalysts on chitosan as a common substrate is presented. Chitosan, accommodating many metal catalysts, is grafted onto the microchannel surface as nanobrush. The versatility, catalytic efficiency, and stability/durability of the microreactor are demonstrated for a number of organic transformations involving various metal compounds as catalysts. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis of novel cellulose- based antibacterial composites of Ag nanoparticles@ metal-organic frameworks@ carboxymethylated fibers.

PubMed

Duan, Chao; Meng, Jingru; Wang, Xinqi; Meng, Xin; Sun, Xiaole; Xu, Yongjian; Zhao, Wei; Ni, Yonghao

2018-08-01

A novel cellulose-based antibacterial material, namely silver nanoparticles@ metal-organic frameworks@ carboxymethylated fibers composites (Ag NPs@ HKUST-1@ CFs), was synthesized. The results showed that the metal-organic frameworks (HKUST-1) were uniformly anchored on the fiber's surfaces by virtue of complexation between copper ions in HKUST-1 and carboxyl groups on the carboxymethylated fibers (CFs). The silver nanoparticles (Ag NPs) were immobilized and well-dispersed into the pores and/or onto the surfaces of HKUST-1 via in situ microwave reduction, resulting in the formation of novel Ag NPs@ HKUST-1@ CFs composites. The antibacterial assays showed that the as-prepared composites exhibited a much higher antibacterial activity than Ag NPs@ CFs or HKUST-1@ CFs samples. Copyright © 2018 Elsevier Ltd. All rights reserved.

Synthesis and characterization of organic/inorganic heterostructure films for hybrid light emitting diode

NASA Astrophysics Data System (ADS)

Toyama, Toshihiko; Ichihara, Tokuyuki; Yamaguchi, Daisuke; Okamoto, Hiroaki

2007-10-01

Thin-film light emitting devices based on organic materials have been gathering attentions for applying a flat-panel display and a solid-state lighting. Alternatively, inorganic technologies such as Si-based thin-film technology have been growing almost independently. It is then expected that combining the Si-based thin-film technology with the organic light emitting diode (OLED) technology will develop innovative devices. Here, we report syntheses of the hybrid light emitting diode (LED) with a heterostructure consisting of p-type SiC x and tris-(8-hydroxyquinoline) aluminum films and characterization for the hybrid LEDs. We present the energy diagram of the heterostructure, and describe that the use of high dark conductivities of the p-type SiC x as well as inserting wide-gap intrinsic a-SiC x at the p-type SiC x/Alq interface are effective for improving device performance.

Synthesis and Characterization of Dipolar Organic Molecules for Nonlinear Optical Materials

DTIC Science & Technology

1992-05-08

BH3, THF; then, aqueous NaOH; ii. pyridinium chlorochromate , methylene chloride; iii. lithium diisopropylamide, THF 50 effective. After purification... pyridinium chlorochromate (1.5 g, 6.96 mmol) was added. The solution was stirred at room temperature for 48 hours. The organic solution was decanted from...the alcohol was oxidized to the aldehyde. Swern oxidation5 was first attempted but gave very low yield in our hands. Alternatively, pyridinium chloro

Synthesis of bioactive organic-inorganic nanohybrid for bone repair through sol-gel processing.

PubMed

Miyazaki, Toshiki; Ohtsuki, Chikara; Tanihara, Masao

2003-12-01

So-called bioactive ceramics have been attractive because they form bone-like apatite on their surfaces to bond directly to living bone when implanted in bony defects. However, they are much more brittle and much less flexible than natural bone. Organic-inorganic hybrids consisting of flexible organic polymers and the essential constituents of the bioactive ceramics (i.e., Si-OH groups and Ca2+ ions) are useful as novel bone substitutes, because of their bioactivity and mechanical properties analogous to those of natural bone. In the present study, organic-inorganic nanohybrids were synthesized from hydroxyethylmethacrylate (HEMA) and methacryloxypropyltrimethoxysilane (MPS), as well as various calcium salts. Bioactivity of the synthesized hybrids was assessed in vitro by examining their acceptance of apatite deposition in simulated body fluid (Kokubo solution). The prepared hybrids formed apatite in Kokubo solution when they were modified with calcium chloride (CaCl2) at 5 or 10 mol% of the total of MPS and HEMA. Deposition of a kind of calcium phosphate was observed for the hybrids modified with calcium acetate (Ca(CH3COO)2), although it could not be identified with apatite. The addition of glycerol up to 10 mol% of the total of MPS and HEMA or water up to 20 mol% as plasticizers did not appreciably decrease the acceptance of apatite formation of the hybrids. These findings allow wide selectivity in the design of bioactive nanohybrids developed by organic modification of the Si-OH group and calcium ion through sol-gel processing. Such nanohybrids have potential as novel bone substitutes with both high bioactivity and high flexibility.

Facile microwave-assisted synthesis of titanium dioxide decorated graphene nanocomposite for photodegradation of organic dyes

SciTech Connect

Gayathri, Shunmugiah; Kottaisamy, Muniasamy; Ramakrishnan, Veerabahu, E-mail: vr.optics1@gmail.com

2015-12-15

An efficient and facile method was adopted to prepare TiO{sub 2}-graphene (TG) nanocomposites with TiO{sub 2} nanoparticles uniformly distributed on graphene. By adjusting the amount of TiO{sub 2} precursor, both high and low dense TiO{sub 2} nanoparticles on graphene were effectively attained via electrostatic attraction between graphene oxide sheets and TiO{sub 2} nanoparticles. The prepared nanocomposites were characterized by various characterization techniques. The TG nanocomposite showed an excellent activity for the photodegradation of the organic dyes such as methylene blue (MB) and rose bengal (RB) under ultra violet (UV) light irradiation. The TG nanocomposite of TG 2.5 showed better photocatalyticmore » performance than bare TiO{sub 2} nanoparticles and other composites. The enhanced activity of the composite material is attributed to the reduction in charge recombination and interaction of organic dyes with graphene. The decrease in charge recombination was evidenced from the photoluminescence (PL) spectra. The observed results suggest that the synthesized TG composites have a potential application to treat the industrial effluents, which contain organic dyes.« less

Synthesis and characterization of the removal of organic pollutants in effluents.

PubMed

Bakayoko, Moussa; Kalakodio, Loissi; Kalagodio, Adiara; Abo, Bodjui Olivier; Muhoza, Jean Pierre; Ismaila, El Moctar

2018-06-27

The use of a large number of organic pollutants results in the accumulation of effluents at the places of production and the environment. These substances are, therefore, dangerous for living organisms and can cause heavy environmental damage. Hence, to cure these problems certain methods were used for the elimination of organic effluents. Indeed, the methods of elimination through magnetic adsorption and/or separation prove to be effective in the treatment of certain wastes, but the effectiveness of each one of these methods depends on several characteristics and also present limitations according to the pollutants they adsorb. This review examines on the one hand the capacity of certain elements of these methods in the elimination of certain pollutants and on the other hand the advantages and limits of these methods. Elements like biochars, biosorbents and composite materials are used due to their very strong porosity which makes it possible for them to develop an important contact surface with the external medium, at low costs, and the possibility of producing them from renewable sources. The latter still run up however against the problems of formation of mud and regeneration. Depollution by magnetic separation is also used due to its capacity to mitigate the disadvantages of certain methods which generally lead to the formation of mud and overcoming also the difficulties like obtaining an active material and at the same time being able to fix the pollutants present in the effluents to treat and sensitize them to external magnetic fields.

Nanoarmored Enzymes for Organic Enzymology: Synthesis and Characterization of Poly(2-Alkyloxazoline)-Enzyme Conjugates.

PubMed

Leurs, Melanie; Tiller, Joerg C

2017-01-01

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.

Polyfluorinated substances in abiotic standard reference materials

EPA Science Inventory

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, meth...

Organic synthesis: the art and science of replicating the molecules of living nature and creating others like them in the laboratory.

PubMed

Nicolaou, K C

2014-03-08

Synthetic organic chemists have the power to replicate some of the most intriguing molecules of living nature in the laboratory and apply their developed synthetic strategies and technologies to construct variations of them. Such molecules facilitate biology and medicine, as they often find uses as biological tools and drug candidates for clinical development. In addition, by employing sophisticated catalytic reactions and appropriately designed synthetic processes, they can synthesize not only the molecules of nature and their analogues, but also myriad other organic molecules for potential applications in many areas of science, technology and everyday life. After a short historical introduction, this article focuses on recent advances in the field of organic synthesis with demonstrative examples of total synthesis of complex bioactive molecules, natural or designed, from the author's laboratories, and their impact on chemistry, biology and medicine.

Organic synthesis: the art and science of replicating the molecules of living nature and creating others like them in the laboratory

PubMed Central

Nicolaou, K. C.

2014-01-01

Synthetic organic chemists have the power to replicate some of the most intriguing molecules of living nature in the laboratory and apply their developed synthetic strategies and technologies to construct variations of them. Such molecules facilitate biology and medicine, as they often find uses as biological tools and drug candidates for clinical development. In addition, by employing sophisticated catalytic reactions and appropriately designed synthetic processes, they can synthesize not only the molecules of nature and their analogues, but also myriad other organic molecules for potential applications in many areas of science, technology and everyday life. After a short historical introduction, this article focuses on recent advances in the field of organic synthesis with demonstrative examples of total synthesis of complex bioactive molecules, natural or designed, from the author’s laboratories, and their impact on chemistry, biology and medicine. PMID:24611027

Design and synthesis of molecular donors for solution-processed high-efficiency organic solar cells.

PubMed

Coughlin, Jessica E; Henson, Zachary B; Welch, Gregory C; Bazan, Guillermo C

2014-01-21

Organic semiconductors incorporated into solar cells using a bulk heterojunction (BHJ) construction show promise as a cleaner answer to increasing energy needs throughout the world. Organic solar cells based on the BHJ architecture have steadily increased in their device performance over the past two decades, with power conversion efficiencies reaching 10%. Much of this success has come with conjugated polymer/fullerene combinations, where optimized polymer design strategies, synthetic protocols, device fabrication procedures, and characterization methods have provided significant advancements in the technology. More recently, chemists have been paying particular attention to well-defined molecular donor systems due to their ease of functionalization, amenability to standard organic purification and characterization methods, and reduced batch-to-batch variability compared to polymer counterparts. There are several critical properties for efficient small molecule donors. First, broad optical absorption needs to extend towards the near-IR region to achieve spectral overlap with the solar spectrum. Second, the low lying highest occupied molecular orbital (HOMO) energy levels need to be between -5.2 and -5.5 eV to ensure acceptable device open circuit voltages. Third, the structures need to be relatively planar to ensure close intermolecular contacts and high charge carrier mobilities. And last, the small molecule donors need to be sufficiently soluble in organic solvents (≥10 mg/mL) to facilitate solution deposition of thin films of appropriate uniformity and thickness. Ideally, these molecules should be constructed from cost-effective, sustainable building blocks using established, high yielding reactions in as few steps as possible. The structures should also be easy to functionalize to maximize tunability for desired properties. In this Account, we present a chronological description of our thought process and design strategies used in the development of highly

An Ribonuclease T2 Family Protein Modulates Acinetobacter baumannii Abiotic Surface Colonization

PubMed Central

Jacobs, Anna C.; Blanchard, Catlyn E.; Catherman, Seana C.; Dunman, Paul M.; Murata, Yoshihiko

2014-01-01

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. PMID:24489668

Synthesis and characterization of low viscosity carbon dioxide binding organic liquids for flue gas clean up

SciTech Connect

Koech, Phillip K.; Malhotra, Deepika; Heldebrant, David J.

2015-01-01

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 CO2more » 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.« less

Soluble Flavanthrone Derivatives: Synthesis, Characterization, and Application to Organic Light-Emitting Diodes.

PubMed

Kotwica, Kamil; Bujak, Piotr; Data, Przemyslaw; Krzywiec, Wojciech; Wamil, Damian; Gunka, Piotr A; Skorka, Lukasz; Jaroch, Tomasz; Nowakowski, Robert; Pron, Adam; Monkman, Andrew

2016-06-01

Simple modification of benzo[h]benz[5,6]acridino[2,1,9,8-klmna]acridine-8,16-dione, an old and almost-forgotten vat dye, by reduction of its carbonyl groups and subsequent O-alkylation, yields solution-processable, electroactive, conjugated compounds of the periazaacene type, suitable for the use in organic electronics. Their electrochemically determined ionization potential and electron affinity of about 5.2 and -3.2 eV, respectively, are essentially independent of the length of the alkoxyl substituent and in good agreement with DFT calculations. The crystal structure of 8,16-dioctyloxybenzo[h]benz[5,6]acridino[2,1,9,8-klmna]acridine (FC-8), the most promising compound, was solved. It crystallizes in space group P1‾ and forms π-stacked columns held together in the 3D structure by dispersion forces, mainly between interdigitated alkyl chains. Molecules of FC-8 have a strong tendency to self-organize in monolayers deposited on a highly oriented pyrolytic graphite surface, as observed by STM. 8,16-Dialkoxybenzo[h]benz[5,6]acridino[2,1,9,8-klmna]acridines are highly luminescent, and all have photoluminescence quantum yields of about 80 %. They show efficient electroluminescence, and can be used as guest molecules with a 4,4'-bis(N-carbazolyl)-1,1'-biphenyl host in guest/host-type organic light-emitting diodes. The best fabricated diodes showed a luminance of about 1900 cd m(-12) , a luminance efficiency of about 3 cd A(-1) , and external quantum efficiencies exceeding 0.9 %. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis and Characterization of Organic Dyes Containing Various Donors and Acceptors

PubMed Central

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

2010-01-01

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

Synthesis, characterization and catalytic activity of novel large network polystyrene-immobilized organic bases