Isotopic exchange of carbon-bound hydrogen over geologic timescales

NASA Astrophysics Data System (ADS)

Sessions, Alex L.; Sylva, Sean P.; Summons, Roger E.; Hayes, John M.

2004-04-01

The increasing popularity of compound-specific hydrogen isotope (D/H) analyses for investigating sedimentary organic matter raises numerous questions about the exchange of carbon-bound hydrogen over geologic timescales. Important questions include the rates of isotopic exchange, methods for diagnosing exchange in ancient samples, and the isotopic consequences of that exchange. This article provides a review of relevant literature data along with new data from several pilot studies to investigate such issues. Published experimental estimates of exchange rates between organic hydrogen and water indicate that at warm temperatures (50-100°C) exchange likely occurs on timescales of 104 to 108 yr. Incubation experiments using organic compounds and D-enriched water, combined with compound-specific D/H analyses, provide a new and highly sensitive method for measuring exchange at low temperatures. Comparison of δD values for isoprenoid and n-alkyl carbon skeletons in sedimentary organic matter provides no evidence for exchange in young (<1 Ma), cool sediments, but strong evidence for exchange in ancient (>350 Ma) rocks. Specific rates of exchange are probably influenced by the nature and abundance of organic matter, pore-water chemistry, the presence of catalytic mineral surfaces, and perhaps even enzymatic activity. Estimates of equilibrium fractionation factors between organic H and water indicate that typical lipids will be depleted in D relative to water by ∼75 to 140‰ at equilibrium (30°C). Thus large differences in δD between organic molecules and water cannot be unambiguously interpreted as evidence against hydrogen exchange. A better approach may be to use changes in stereochemistry as a proxy for hydrogen exchange. For example, estimated rates of H exchange in pristane are similar to predicted rates for stereochemical inversion in steranes and hopanes. The isotopic consequences of this exchange remain in question. Incubations of cholestene with D2O indicate that the number of D atoms incorporated during structural rearrangements can be far less than the number of C-H bonds that are broken. Sample calculations indicate that, for steranes in immature sediments, the D/H ratio imparted by biosynthesis may be largely preserved in spite of significant structural changes.

Site-Specific Hydrogen Isotope Composition of Propane: Mass spectrometric methods, equilibrium temperature dependence, and kinetics of exchange

NASA Astrophysics Data System (ADS)

Xie, H.; Ponton, C.; Kitchen, N.; Lloyd, M. K.; Lawson, M.; Formolo, M. J.; Eiler, J. M.

2016-12-01

Intramolecular isotope ordering can constrain temperatures of synthesis, mechanisms of formation, and/or source substrates of organic compounds. Here we explore site-specific hydrogen isotope variations of propane. Statistical thermodynamic models predict that at equilibrium methylene hydrogen (-CH2-) in propane will be 10's of per mil higher in D/H ratio than methyl hydrogen (-CH3) at geologically relevant temperatures, and that this difference is highly temperature dependent ( 0.5-1 ‰/°C). Chemical-kinetic controls on site-specific D/H in propane could constrain the mechanisms, conditions and extents of propane synthesis or destruction. We have developed a method for measuring the difference in D/H ratio between methylene and methyl hydrogen in propane by gas source mass spectrometry. The data were measured using the Thermo Fisher Double Focusing Sector high resolution mass spectrometer (DFS), and involve comparison of the D/H ratios of molecular ion (C3H8+) and the ethyl fragmental ion (C2H5+). We demonstrate the accuracy and precision of this method through analysis of D-labeled and independently analyzed propanes. In the exchange experiments, propane was heated (100-200 oC) either alone or in the presence of D-enriched water (δD=1,1419 ‰ SMOW), with or without one of several potentially catalytic substrates for hours to weeks. Propane was found to exchange hydrogen with water vigorously at 200 °C in the presence of metal catalysts. In the presence of Ni catalyst, methylene hydrogen exchanges 2.5 times faster than methyl hydrogen. Hydrogen exchange in the presence of Pd catalyst is more effective and can equilibrate hydrogen isotope distribution on propane on the order of 7 days. Isotopic exchange in the presence of natural materials have also been tested, but is only measurable in the methylene group at 200 °C. High catalytic activity of Pd permits attainment of a bracketed, time-invariant equilibrium state that we use to calibrate the site-specific thermometer; these experiments also provide a reference frame for reporting mass spectrometric data. Differential H-exchange rates of the two molecular sites in propane could be a new tool to constrain thermal history of sub-surface propane. Our experimental and mass spectrometric approaches should be generalizable to other hydrocarbon compounds.

Hydrogen Isotope Fractionation As a Tool to Identify Aerobic and Anaerobic PAH Biodegradation.

PubMed

Kümmel, Steffen; Starke, Robert; Chen, Gao; Musat, Florin; Richnow, Hans H; Vogt, Carsten

2016-03-15

Aerobic and anaerobic polycyclic aromatic hydrocarbon (PAH) biodegradation was characterized by compound specific stable isotope analysis (CSIA) of the carbon and hydrogen isotope effects of the enzymatic reactions initiating specific degradation pathways, using naphthalene and 2-methylnaphtalene as model compounds. Aerobic activation of naphthalene and 2-methylnaphthalene by Pseudomonas putida NCIB 9816 and Pseudomonas fluorescens ATCC 17483 containing naphthalene dioxygenases was associated with moderate carbon isotope fractionation (εC = -0.8 ± 0.1‰ to -1.6 ± 0.2‰). In contrast, anaerobic activation of naphthalene by a carboxylation-like mechanism by strain NaphS6 was linked to negligible carbon isotope fractionation (εC = -0.2 ± 0.2‰ to -0.4 ± 0.3‰). Notably, anaerobic activation of naphthalene by strain NaphS6 exhibited a normal hydrogen isotope fractionation (εH = -11 ± 2‰ to -47 ± 4‰), whereas an inverse hydrogen isotope fractionation was observed for the aerobic strains (εH = +15 ± 2‰ to +71 ± 6‰). Additionally, isotope fractionation of NaphS6 was determined in an overlaying hydrophobic carrier phase, resulting in more reliable enrichment factors compared to immobilizing the PAHs on the bottle walls without carrier phase. The observed differences especially in hydrogen fractionation might be used to differentiate between aerobic and anaerobic naphthalene and 2-methylnaphthalene biodegradation pathways at PAH-contaminated field sites.

Sphalerite is a geochemical catalyst for carbon−hydrogen bond activation

PubMed Central

Shipp, Jessie A.; Gould, Ian R.; Shock, Everett L.; Williams, Lynda B.; Hartnett, Hilairy E.

2014-01-01

Reactions among minerals and organic compounds in hydrothermal systems are critical components of the Earth’s deep carbon cycle, provide energy for the deep biosphere, and may have implications for the origins of life. However, there is limited information as to how specific minerals influence the reactivity of organic compounds. Here we demonstrate mineral catalysis of the most fundamental component of an organic reaction: the breaking and making of a covalent bond. In the absence of mineral, hydrothermal reaction of cis- and trans-1,2-dimethylcyclohexane is extremely slow and generates many products. In the presence of sphalerite (ZnS), however, the reaction rate increases dramatically and one major product is formed: the corresponding stereoisomer. Isotope studies show that the sphalerite acts as a highly specific heterogeneous catalyst for activation of a single carbon−hydrogen bond in the dimethylcyclohexanes. PMID:25071186

Sphalerite is a geochemical catalyst for carbon-hydrogen bond activation.

PubMed

Shipp, Jessie A; Gould, Ian R; Shock, Everett L; Williams, Lynda B; Hartnett, Hilairy E

2014-08-12

Reactions among minerals and organic compounds in hydrothermal systems are critical components of the Earth's deep carbon cycle, provide energy for the deep biosphere, and may have implications for the origins of life. However, there is limited information as to how specific minerals influence the reactivity of organic compounds. Here we demonstrate mineral catalysis of the most fundamental component of an organic reaction: the breaking and making of a covalent bond. In the absence of mineral, hydrothermal reaction of cis- and trans-1,2-dimethylcyclohexane is extremely slow and generates many products. In the presence of sphalerite (ZnS), however, the reaction rate increases dramatically and one major product is formed: the corresponding stereoisomer. Isotope studies show that the sphalerite acts as a highly specific heterogeneous catalyst for activation of a single carbon-hydrogen bond in the dimethylcyclohexanes.

Impact of Lactic Acid and Hydrogen Ion on the Simultaneous Fermentation of Glucose and Xylose by the Carbon Catabolite Derepressed Lactobacillus brevis ATCC 14869.

PubMed

Jeong, Kyung Hun; Israr, Beenish; Shoemaker, Sharon P; Mills, David A; Kim, Jaehan

2016-07-28

Lactobacillus brevis ATCC 14869 exhibited a carbon catabolite de-repressed (CCR) phenotype which has ability to consume fermentable sugar simultaneously with glucose. To evaluate this unusual phenotype under harsh conditions during fermentation, the effect of lactic acid and hydrogen ion concentrations on L. brevis ATCC 14869 were examined. Kinetic equations describing the relationship between specific cell growth rate and lactic acid or hydrogen ion concentration has been reduced. The change of substrate utilization and product formation according to lactic acid and hydrogen ion concentration in the media were quantitatively described. Moreover; utilization of other compounds were also observed along with hydrogen ion and lactic acid concentration simultaneously. It has been found that substrate preference changes significantly regarding to utilization of compounds in media. That could result into formation of two-carbon products. In particular, acetic acid present in the media as sodium acetate were consumed by L. brevis ATCC 14869 under extreme pH of both acid and alkaline conditions.

Photoredox-catalyzed deuteration and tritiation of pharmaceutical compounds

PubMed Central

Loh, Yong Yao; Nagao, Kazunori; Hoover, Andrew J.; Hesk, David; Rivera, Nelo R.; Colletti, Steven L.; Davies, Ian W.; MacMillan, David W. C.

2018-01-01

Deuterium- and tritium-labeled pharmaceutical compounds are pivotal diagnostic tools in drug discovery research, providing vital information about the biological fate of drugs and drug metabolites. Herein we demonstrate that a photoredox-mediated hydrogen atom transfer protocol can efficiently and selectively install deuterium (D) and tritium (T) at α-amino sp3 carbon-hydrogen bonds in a single step, using isotopically labeled water (D2O or T2O) as the source of hydrogen isotope. In this context, we also report a convenient synthesis of T2O from T2, providing access to high-specific-activity T2O. This protocol has been successfully applied to the high incorporation of deuterium and tritium in 18 drug molecules, which meet the requirements for use in ligand-binding assays and absorption, distribution, metabolism, and excretion studies. PMID:29123019

Palladium catalyzed hydrogenation of bio-oils and organic compounds

DOEpatents

Elliott, Douglas C [Kennewick, WA; Hu, Jianli [Richland, WA; Hart,; Todd, R [Kennewick, WA; Neuenschwander, Gary G [Burbank, WA

2011-06-07

The invention provides palladium-catalyzed hydrogenations of bio-oils and certain organic compounds. Experimental results have shown unexpected and superior results for palladium-catalyzed hydrogenations of organic compounds typically found in bio-oils.

Palladium catalyzed hydrogenation of bio-oils and organic compounds

DOEpatents

Elliott, Douglas C [Richland, WA; Hu, Jianli [Kennewick, WA; Hart, Todd R [Kennewick, WA; Neuenschwander, Gary G [Burbank, WA

2008-09-16

The invention provides palladium-catalyzed hydrogenations of bio-oils and certain organic compounds. Experimental results have shown unexpected and superior results for palladium-catalyzed hydrogenations of organic compounds typically found in bio-oils.

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

Moran, James J.; Kreuzer, Helen W.; Carman, April J.

Acid scavengers are frequently used as stabilizer compounds in a variety of applications. When used to stabilize volatile compounds such as nerve agents, the lower volatility and higher stability of acid scavengers make them more persistent in a post-event forensic setting. We are employing compound-specific stable isotope analysis of the carbon, nitrogen, and hydrogen components of three acid scavenging compounds (N,N-diethylaniline, tributylamine, and triethylamine) as a tool for distinguishing between different samples of the stabilizers. Combined analysis of three stable isotopes in these samples improves the technique’s resolving potential, enhancing sample matching capabilities. The compound specific methods developed here canmore » be applied to instances where these compounds are not pure, such as when mixed with an agent or when found as a residue at an event site. Effective sample matching can be crucial for linking compounds at multiple event sites or linking a supply inventory to an event.« less

Mechanical alloying of a hydrogenation catalyst used for the remediation of contaminated compounds

NASA Technical Reports Server (NTRS)

Quinn, Jacqueline W. (Inventor); Geiger, Cherie L. (Inventor); Aitken, Brian S. (Inventor); Clausen, Christian A. (Inventor)

2012-01-01

A hydrogenation catalyst including a base material coated with a catalytic metal is made using mechanical milling techniques. The hydrogenation catalysts are used as an excellent catalyst for the dehalogenation of contaminated compounds and the remediation of other industrial compounds. Preferably, the hydrogenation catalyst is a bimetallic particle including zero-valent metal particles coated with a catalytic material. The mechanical milling technique is simpler and cheaper than previously used methods for producing hydrogenation catalysts.

Mechanical alloying of a hydrogenation catalyst used for the remediation of contaminated compounds

NASA Technical Reports Server (NTRS)

Quinn, Jacqueline W. (Inventor); Aitken, Brian S. (Inventor); Clausen, Christian A. (Inventor); Geiger, Cherie L. (Inventor)

2010-01-01

A hydrogenation catalyst including a base material coated with a catalytic metal is made using mechanical milling techniques. The hydrogenation catalysts are used as an excellent catalyst for the dehalogenation of contaminated compounds and the remediation of other industrial compounds. Preferably, the hydrogenation catalyst is a bimetallic particle including zero-valent metal particles coated with a catalytic material. The mechanical milling technique is simpler and cheaper than previously used methods for producing hydrogenation catalysts.

High-pressure/low-temperature neutron scattering of gas inclusion compounds: Progress and prospects

PubMed Central

Zhao, Yusheng; Xu, Hongwu; Daemen, Luke L.; Lokshin, Konstantin; Tait, Kimberly T.; Mao, Wendy L.; Luo, Junhua; Currier, Robert P.; Hickmott, Donald D.

2007-01-01

Alternative energy resources such as hydrogen and methane gases are becoming increasingly important for the future economy. A major challenge for using hydrogen is to develop suitable materials to store it under a variety of conditions, which requires systematic studies of the structures, stability, and kinetics of various hydrogen-storing compounds. Neutron scattering is particularly useful for these studies. We have developed high-pressure/low-temperature gas/fluid cells in conjunction with neutron diffraction and inelastic neutron scattering instruments allowing in situ and real-time examination of gas uptake/release processes. We studied the formation of methane and hydrogen clathrates, a group of inclusion compounds consisting of frameworks of hydrogen-bonded H2O molecules with gas molecules trapped inside the cages. Our results reveal that clathrate can store up to four hydrogen molecules in each of its large cages with an intermolecular H2–H2 distance of only 2.93 Å. This distance is much shorter than that in the solid/metallic hydrogen (3.78 Å), suggesting a strong densification effect of the clathrate framework on the enclosed hydrogen molecules. The framework-pressurizing effect is striking and may exist in other inclusion compounds such as metal-organic frameworks (MOFs). Owing to the enormous variety and flexibility of their frameworks, inclusion compounds may offer superior properties for storage of hydrogen and/or hydrogen-rich molecules, relative to other types of compounds. We have investigated the hydrogen storage properties of two MOFs, Cu3[Co(CN)6]2 and Cu3(BTC)2 (BTC = benzenetricarboxylate), and our preliminary results demonstrate that the developed neutron-scattering techniques are equally well suited for studying MOFs and other inclusion compounds. PMID:17389387

Bipyridinium array-type porous polymer displaying hydrogen storage, charge-transfer-type guest inclusion, and tunable magnetic properties.

PubMed

Yao, Qing-Xia; Pan, Long; Jin, Xu-Hui; Li, Jing; Ju, Zhan-Feng; Zhang, Jie

2009-11-09

A multifunctional pillared-layer porous coordination polymer, {[Mn(2)(Bpybc)(ox)(2)]8 H(2)O}(n), has been constructed based on a flexible viologen derivative, 1,1'-bis(4-carboxybenzyl)-4,4'-bipyridinium dichloride (H(2)BpybcCl(2)), and an oxalate (ox) coligand. Single-crystal X-ray analysis reveals that the compound possesses multichannels with dimensions of about 6.1x6.6 A along the [110] and [-110] directions and 4.2x7.6 A along [100], and a void space of about 41.4 %. Hydrogen adsorption measurements at 77 K and 1 atm indicate that the compound exhibits a hydrogen uptake of 0.71 wt %. Owing to the incorporation of bipyridinium acceptor units, the compound can selectively accommodate aromatic donors into its nanosized pores based on charge-transfer interactions in an elastic way, and afford a specific color to different guests. Furthermore, the effect of perturbation exerted by the guest molecules on its magnetic properties has been investigated. The results indicate that the donor inclusion has little effect on its antiferromagnetic behavior, whereas dehydration of the compound decreases the strength of the magnetic exchange couplings and results in a change of the antiferromagnetic transition temperature from 14.7 to 9.8 K.

A ketone/alcohol polymer for cycle of electrolytic hydrogen-fixing with water and releasing under mild conditions

PubMed Central

Kato, Ryo; Yoshimasa, Keisuke; Egashira, Tatsuya; Oya, Takahiro; Oyaizu, Kenichi; Nishide, Hiroyuki

2016-01-01

Finding a safe and efficient carrier of hydrogen is a major challenge. Recently, hydrogenated organic compounds have been studied as hydrogen storage materials because of their ability to stably and reversibly store hydrogen by forming chemical bonds; however, these compounds often suffer from safety issues and are usually hydrogenated with hydrogen at high pressure and/or temperature. Here we present a ketone (fluorenone) polymer that can be moulded as a plastic sheet and fixes hydrogen via a simple electrolytic hydrogenation at −1.5 V (versus Ag/AgCl) in water at room temperature. The hydrogenated alcohol derivative (the fluorenol polymer) reversibly releases hydrogen by heating (80 °C) in the presence of an aqueous iridium catalyst. Both the use of a ketone polymer and the efficient hydrogen fixing with water as a proton source are completely different from other (de)hydrogenated compounds and hydrogenation processes. The easy handling and mouldable polymers could suggest a pocketable hydrogen carrier. PMID:27687772

Reconstructing hydroclimatic variations using compound-specific hydrogen isotope analysis of biomarkers from a maar lake in the Central Highlands, Vietnam

NASA Astrophysics Data System (ADS)

Doiron, Kelsey; Stevens, Lora; Sauer, Peter

2017-04-01

Monsoonal variation in Southeast Asia affects a significant portion of the global population, but knowledge regarding response of the monsoon system to changing boundary conditions is limited. The paleoclimatic tool of compound-specific isotope analysis(CSIA) provides the ability to reconstruct past precipitation using a diverse set of biomarkers preserved in the sedimentary record. Limited proxies in tropical southeast Asia and difficult site access have led to a deficit in paleoclimate records. Ia M'He (14˚ 10'45" N, 107˚ 52' E) is a shallow volcanic crater (maar) lake, approximately 57 ha, located in the Central Highlands of Vietnam. Precipitation in the Central Highlands is sensitive to reorganizations of major climatic features, such as the migration of the ITCZ and the coupled Indo-Asian monsoon, ENSO and related shifts in the Pacific Walker Circulation and typhoon frequency. To examine this complex behavior, this pilot study aims to provide a 500-year record of effective moisture inferred from CSIA of hydrogen isotopes on biomarkers. Carbon/nitrogen ratios and carbon isotope ratios indicate that bulk organic matter is a combination of algae and C3 vegetation, offering the potential to use compound-specific hydrogen isotopes of aquatic and terrestrial organic matter in tandem. Preliminary analysis of the core shows dominant alkane chain lengths of C27 and C29, associated with terrestrial plant leaf waxes. The hydrogen isotope ratios of the plant wax components provide a proxy for paleo precipitation in a region where rainfall and droughts heavily influence population dynamics and create social discord. The CSIA record is expected to correlate with records from northern Vietnam, the South China Sea and Indonesia, with greater precipitation during the Little Ice Age. The degree to which evaporative modification of lake water (i.e., seasonal drying) occurs will be estimated by comparing the terrestrial CSIA values indicative of meteoric water with aquatic CSIA values, which will capture the hydrologic balance of the lake itself.

DFT studies of the vibrational spectra of salicylic acid and related compounds

USDA-ARS?s Scientific Manuscript database

Compounds that exhibit intra- and intermolecular hydrogen bonds can have infrared and Raman spectra that show evidences of these hydrogen bonds. In modeling the vibrational spectra of such compounds, the addition of explicit hydrogen bonding species (e.g. solvent molecules) can often improve agreeme...

2,3-Dihydroxybenzoic acid amides of tetraazaalkanes and tetaaza cycloalkanes

DOEpatents

Weitl, Frederick L. [Martinez, CA; Raymond, Kenneth N. [Berkeley, CA

1980-01-01

A compound of the formula: ##STR1## wherein X is hydrogen or a conventional electron-withdrawing group, particularly --SO.sub.3 H or a salt thereof; n is 2, 3, or 4; m is 2, 3, or 4; and p is 2 or 3. The present compounds are useful as specific sequestering agents for actinide (IV) ions. Also described is a method for the 2,3-dihydroxybenzamidation of azaalkanes.

Catalytic Hydrogenation of Organic Compounds without H2 Supply: An Electrochemical System

ERIC Educational Resources Information Center

Navarro, Daniela Maria do Amaral Ferraz; Navarro, Marcelo

2004-01-01

An experiment developed for an undergraduate organic chemistry laboratory course that can be used to introduce the catalytic hydrogenation reaction, catalysis electrochemical principles and gas chromatography is presented. The organic compounds hydrogenated by the electrocatalytic hydrogenation (ECH) process were styrene, benzaldehyde and…

Quantification of in Situ Biodegradation Rate Constants Using a Novel Combined Isotope Approach

NASA Astrophysics Data System (ADS)

Blum, P.; Sültenfuß, J.; Martus, P.

2014-12-01

Numerous studies have shown the enormous potential of the compound-specific isotope analysis (CSIA) for studying the biodegradation of organic compounds such as monoaromatic hydrocarbons (BTEX), polyaromatic hydrocarbons (PAH), chlorinated solvents and other organic contaminants and environmental transformation mechanisms in groundwater. In addition, two-dimensional isotope analysis such as carbon and hydrogen have been successfully studied indicating the potential to also investigate site-specific reaction mechanisms. The main objective of the current study however is to quantify real effective in situ biodegradation rate constants in a coal-tar contaminated aquifer by combining compound-specific isotope analysis (CSIA) and tracer-based (3H-3He) ground-water dating (TGD). Hence, groundwater samples are used to determine groundwater residence times, and carbon and hydrogen stable isotopes are analyzed for selected BTEX and PAH. The results of the hydrogen stable isotopes surprisingly indicate no isotope fractionation and therefore no biodegradation. In contrast, for stable carbon isotopes of selected BTEX such as o-xylene and toluene, isotope shifts are detected indicating active biodegradation under sulfate-reducing conditions. These and previous results of stable carbon isotopes show that only for o-xylene a clear evidence for biodegradation is possible for the studied site. Nevertheless, in combining these results with the groundwater residence times, which range between 1 year for the shallow wells (20 m below surface) and 41 years for the deeper wells (40 m below surface), it is feasible to effectively determine in situ biodegradation rate constants for o-xylene. Conversely, the outcome also evidently demonstrate the major limitations of the novel combined isotope approach for a successful implementation of monitored natural attenuation (MNA) at such field sites.

Magnetically Recoverable Supported Ruthenium Catalyst for Hydrogenation of Alkynes and Transfer Hydrogenation of Carbonyl Compounds

EPA Science Inventory

A ruthenium (Ru) catalyst supported on magnetic nanoparticles (NiFe2O4) has been successfully synthesized and used for hydrogenation of alkynes at room temperature as well as transfer hydrogenation of a number of carbonyl compounds under microwave irradiation conditions. The cata...

Quantifying hydrogen-deuterium exchange of meteoritic dicarboxylic acids during aqueous extraction

NASA Astrophysics Data System (ADS)

Fuller, M.; Huang, Y.

2003-03-01

Hydrogen isotope ratios of organic compounds in carbonaceous chondrites provide critical information about their origins and evolutionary history. However, because many of these compounds are obtained by aqueous extraction, the degree of hydrogen-deuterium (H/D) exchange that occurs during the process needs to be quantitatively evaluated. This study uses compound- specific hydrogen isotopic analysis to quantify the H/D exchange during aqueous extraction. Three common meteoritic dicarboxylic acids (succinic, glutaric, and 2-methyl glutaric acids) were refluxed under conditions simulating the extraction process. Changes in D values of the dicarboxylic acids were measured following the reflux experiments. A pseudo-first order rate law was used to model the H/D exchange rates which were then used to calculate the isotope exchange resulting from aqueous extraction. The degree of H/D exchange varies as a result of differences in molecular structure, the alkalinity of the extraction solution and presence/absence of meteorite powder. However, our model indicates that succinic, glutaric, and 2-methyl glutaric acids with a D of 1800 would experience isotope changes of 38, 10, and 6, respectively during the extraction process. Therefore, the overall change in D values of the dicarboxylic acids during the aqueous extraction process is negligible. We also demonstrate that H/D exchange occurs on the chiral -carbon in 2-methyl glutaric acid. The results suggest that the racemic mixture of 2-methyl glutaric acid in the Tagish Lake meteorite could result from post-synthesis aqueous alteration. The approach employed in this study can also be used to quantify H/D exchange for other important meteoritic compounds such as amino acids.

Process for preparing 2,3-dihydroxybenzoic acid amides of tetraazaalkanes and cycloalkanes

DOEpatents

Weitl, Frederick L.; Raymond, Kenneth N.

1985-01-01

A compound of the formula: ##STR1## wherein X is hydrogen or a conventional electron-withdrawing group, particularly --SO.sub.3 H or a salt thereof; n is 2, 3, or 4; m is 2, 3, or 4; and p is 2 or 3. The present compounds are useful as specific sequestering agents for actinide (IV) ions. Also described is a method for the 2,3-dihydroxybenzamidation of azaalkanes.

Atomic hydrogen storage method and apparatus

NASA Technical Reports Server (NTRS)

Woollam, J. A. (Inventor)

1978-01-01

Atomic hydrogen, for use as a fuel or as an explosive, is stored in the presence of a strong magnetic field in exfoliated layered compounds such as molybdenum disulfide or an elemental layer material such as graphite. The compound is maintained at liquid helium temperatures and the atomic hydrogen is collected on the surfaces of the layered compound which are exposed during delamination (exfoliation). The strong magnetic field and the low temperature combine to prevent the atoms of hydrogen from recombining to form molecules.

Atomic hydrogen storage method and apparatus

NASA Technical Reports Server (NTRS)

Woollam, J. A. (Inventor)

1980-01-01

Atomic hydrogen, for use as a fuel or as an explosive, is stored in the presence of a strong magnetic field in exfoliated layered compounds such as molybdenum disulfide or an elemental layer material such as graphite. The compounds maintained at liquid helium temperatures and the atomic hydrogen is collected on the surfaces of the layered compound which are exposed during delamination (exfoliation). The strong magnetic field and the low temperature combine to prevent the atoms of hydrogen from recombining to form molecules.

Atomic hydrogen storage. [cryotrapping and magnetic field strength

NASA Technical Reports Server (NTRS)

Woollam, J. A. (Inventor)

1980-01-01

Atomic hydrogen, for use as a fuel or as an explosive, is stored in the presence of a strong magnetic field in exfoliated layered compounds such as molybdenum disulfide or an elemental layer material such as graphite. The compound is maintained at liquid temperatures and the atomic hydrogen is collected on the surfaces of the layered compound which are exposed during delamination (exfoliation). The strong magnetic field and the low temperature combine to prevent the atoms of hydrogen from recombining to form molecules.

A Specific Nucleophilic Ring-Opening Reaction of Aziridines as a Unique Platform for the Construction of Hydrogen Polysulfides Sensors

DOE PAGES

Chen, Wei; Rosser, Ethan W.; Zhang, Di; ...

2015-05-11

Hydrogen polysulfides (H 2S n, n>1) have been recently suggested to be the actual signalling molecules that involved in sulfur-related redox biology. However the exact mechanisms of H 2S n are still poorly understood and a major hurdle in this field is the lack of reliable and convenient methods for H 2S n detection. In this work we report a unique ring-opening reaction of N-sulfonylaziridine by Na 2S 2 under mild conditions. Based on this reaction a novel H 2S n-specific fluorescent probe (AP) was developed. The probe showed high sensitivity and selectivity for H 2S n. Notably, the fluorescentmore » turn-on product, i.e. compound 1, exhibited excellent two-photon photophysical properties and a large Stokes shift. Moreover, the high solid state luminescent efficiency of compound 1 makes it a potential candidate for organic emitters and solid-state lighting devices.« less

Ion Mobility Spectrometry-Mass Spectrometry Coupled with Gas-Phase Hydrogen/Deuterium Exchange for Metabolomics Analyses

NASA Astrophysics Data System (ADS)

Maleki, Hossein; Karanji, Ahmad K.; Majuta, Sandra; Maurer, Megan M.; Valentine, Stephen J.

2018-02-01

Ion mobility spectrometry-mass spectrometry (IMS-MS) in combination with gas-phase hydrogen/deuterium exchange (HDX) and collision-induced dissociation (CID) is evaluated as an analytical method for small-molecule standard and mixture characterization. Experiments show that compound ions exhibit unique HDX reactivities that can be used to distinguish different species. Additionally, it is shown that gas-phase HDX kinetics can be exploited to provide even further distinguishing capabilities by using different partial pressures of reagent gas. The relative HDX reactivity of a wide variety of molecules is discussed in light of the various molecular structures. Additionally, hydrogen accessibility scoring (HAS) and HDX kinetics modeling of candidate ( in silico) ion structures is utilized to estimate the relative ion conformer populations giving rise to specific HDX behavior. These data interpretation methods are discussed with a focus on developing predictive tools for HDX behavior. Finally, an example is provided in which ion mobility information is supplemented with HDX reactivity data to aid identification efforts of compounds in a metabolite extract.

Photoredox-catalyzed deuteration and tritiation of pharmaceutical compounds.

PubMed

Loh, Yong Yao; Nagao, Kazunori; Hoover, Andrew J; Hesk, David; Rivera, Nelo R; Colletti, Steven L; Davies, Ian W; MacMillan, David W C

2017-12-01

Deuterium- and tritium-labeled pharmaceutical compounds are pivotal diagnostic tools in drug discovery research, providing vital information about the biological fate of drugs and drug metabolites. Herein we demonstrate that a photoredox-mediated hydrogen atom transfer protocol can efficiently and selectively install deuterium (D) and tritium (T) at α-amino sp 3 carbon-hydrogen bonds in a single step, using isotopically labeled water (D 2 O or T 2 O) as the source of hydrogen isotope. In this context, we also report a convenient synthesis of T 2 O from T 2 , providing access to high-specific-activity T 2 O. This protocol has been successfully applied to the high incorporation of deuterium and tritium in 18 drug molecules, which meet the requirements for use in ligand-binding assays and absorption, distribution, metabolism, and excretion studies. Copyright © 2017 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works.

Kinetics and thermochemistry of 2,5-dimethyltetrahydrofuran and related oxolanes: next next-generation biofuels.

PubMed

Simmie, John M

2012-05-10

The enthalpies of formation, entropies, specific heats at constant pressure, enthalpy functions, and all carbon-hydrogen and carbon-methyl bond dissociation energies have been computed using high-level methods for the cyclic ethers (oxolanes) tetrahydrofuran, 2-methyltetrahydrofuran, and 2,5-dimethyltetrahydrofuran. Barrier heights for hydrogen-abstraction reactions by hydrogen atoms and the methyl radical are also computed and shown to correlate with reaction energy change. The results show a pleasing consistency and considerably expands the available data for these important compounds. Abstraction by ȮH is accompanied by formation of both pre- and postreaction weakly bound complexes. The resulting radicals formed after abstraction undergo ring-opening reactions leading to readily recognizable intermediates, while competitive H-elimination reactions result in formation of dihydrofurans. Formation enthalpies of all 2,3- and 2,5-dihydrofurans and associated radicals are also reported. It is probable that the compounds at the center of this study will be relatively clean-burning biofuels, although formation of intermediate aldehydes might be problematic.

Compound Specific Hydrogen Isotope Composition of Type II and III Kerogen Extracted by Pyrolysis-GC-MS-IRMS

NASA Technical Reports Server (NTRS)

Socki, Richard A.; Pernia, Denet; Evans, Michael; Fu, Qi; Bissada, Kadry K.; Curiale, Joseph A.; Niles, Paul B.

2013-01-01

The use of Hydrogen (H) isotopes in understanding oil and gas resource plays is in its infancy. Described here is a technique for H isotope analysis of organic compounds pyrolyzed from oil and gas shale-derived kerogen. Application of this technique will progress our understanding. This work complements that of Pernia et al. (2013, this meeting) by providing a novel method for the H isotope analysis of specific compounds in the characterization of kerogen extracted by analytically diverse techniques. Hydrogen isotope analyses were carried out entirely "on-line" utilizing a CDS 5000 Pyroprobe connected to a Thermo Trace GC Ultra interfaced with a Thermo MAT 253 IRMS. Also, a split of GC-separated products was sent to a DSQ II quadrupole MS to make semi-quantitative compositional measurements of the extracted compounds. Kerogen samples from five different basins (type II and III) were dehydrated (heated to 80 C overnight in vacuum) and analyzed for their H isotope compositions by Pyrolysis-GC-MS-TC-IRMS. This technique takes pyrolysis products separated via GC and reacts them in a high temperature conversion furnace (1450 C) which quantitatively forms H2, following a modified method of Burgoyne and Hayes, (1998, Anal. Chem., 70, 5136-5141). Samples ranging from approximately 0.5 to 1.0mg in size, were pyrolyzed at 800 C for 30s. Compounds were separated on a Poraplot Q GC column. Hydrogen isotope data from all kerogen samples typically show enrichment in D from low to high molecular weight compounds. Water (H2O) average deltaD = -215.2 (V-SMOW), ranging from -271.8 for the Marcellus Shale to -51.9 for the Polish Shale. Higher molecular weight compounds like toluene (C7H8) have an average deltaD of -89.7 0/00, ranging from -156.0 for the Barnett Shale to -50.0 for the Monterey Shale. We interpret these data as representative of potential H isotope exchange between hydrocarbons and sediment pore water during formation within each basin. Since hydrocarbon H isotopes readily exchange with water, these data may provide some useful information on gas-water or oil-water interaction in resource plays, and further as a possible indicator of paleo-environmental conditions. Alternatively, our data may be an indication of H isotope exchange with water and/or acid during the kerogen isolation process. Either of these interpretations will prove useful when deciphering H isotope data derived from kerogen analysis. More experiments are planned to discern these two or other possible scenarios.

Exploring monovalent copper compounds with oxygen and hydrogen

PubMed Central

Korzhavyi, Pavel A.; Soroka, Inna L.; Isaev, Eyvaz I.; Lilja, Christina; Johansson, Börje

2012-01-01

New important applications of copper metal, e.g., in the areas of hydrogen production, fuel cell operation, and spent nuclear fuel disposal, require accurate knowledge of the physical and chemical properties of stable and metastable copper compounds. Among the copper(I) compounds with oxygen and hydrogen, cuprous oxide Cu2O is the only one stable and the best studied. Other such compounds are less known (CuH) or totally unknown (CuOH) due to their instability relative to the oxide. Here we combine quantum-mechanical calculations with experimental studies to search for possible compounds of monovalent copper. Cuprous hydride (CuH) and cuprous hydroxide (CuOH) are proved to exist in solid form. We establish the chemical and physical properties of these compounds, thereby filling the existing gaps in our understanding of hydrogen- and oxygen-related phenomena in Cu metal. PMID:22219370

Ruthenium supported on magnetic nanoparticles: An efficient and recoverable catalyst for hydrogenation of alkynes and transfer hydrogenation of carbonyl compounds

EPA Science Inventory

Ruthenium supported on surface modified magnetic nanoparticles (NiFe2O4) has been successfully synthesized and applied for hydrogenation of alkynes at room temperature as well as transfer hydrogenation of a number of carbonyl compounds under microwave irradiation conditions. The ...

Effect of Nitrooxy Compounds with Different Molecular Structures on the Rumen Methanogenesis, Metabolic Profile, and Methanogenic Community.

PubMed

Jin, Wei; Meng, Zhenxiang; Wang, Jing; Cheng, Yanfen; Zhu, Weiyun

2017-08-01

Rumen in vitro fermentation was used to evaluate the capacity of nitrooxy compounds to mitigate rumen methane production. The following three nitrooxy compounds, each with different molecular structures, were evaluated: 2,2-dimethyl-3-(nitrooxy) propanoic (DNP), N-[2-(Nitrooxy)ethyl]-3-pyridinecarboxamide (NPD), and nitroglycerin (NG). All three compounds substantially decreased the total gas production, methane production, and the acetate:propionate ratio, while increasing hydrogen production. The growth of methanogens was specifically inhibited by all three compounds, without affecting the abundance of bacteria, anaerobic fungi, or protozoa. However, inhibition of methanogenesis required a much higher dose of DNP when compared to NPD or NG. Further investigations were conducted on NG to determine its effects on the methanogenic community. NG reduced the relative abundance of Methanomassiliicoccales, while increasing the relative abundance of Methanobrevibacter and Methanosphaera. Overall, the results suggested that all three of these nitrooxy compounds could specifically inhibit rumen methanogenesis, but NPD and NG were much more efficient than DNP at rumen methane mitigation.

Direct hydrogenation and one-pot reductive amidation of nitro compounds over Pd/ZnO nanoparticles as a recyclable and heterogeneous catalyst

NASA Astrophysics Data System (ADS)

Hosseini-Sarvari, Mona; Razmi, Zahra

2015-01-01

A novel Pd supported on ZnO nanoparticles was readily synthesized and characterized. The amount of palladium on ZnO is 9.84 wt% which was determined by ICP analysis and atomic absorption spectroscopy (AAS). Percentage of accessible Pd as active catalyst is also estimated to 2.72% based on the thermogravimetric (TG) analysis. This nano-sized Pd/ZnO with an average particle size of 20-25 nm and specific surface area 40.61 m2 g-1 was used as a new reusable heterogeneous catalyst for direct hydrogenation and one-pot reductive amidation of nitro compounds without the use of any ligands under atmospheric pressure. The catalyst can be recovered and recycled several times without marked loss of activity.

Hydrogen bonds and antiviral activity of benzaldehyde derivatives

NASA Astrophysics Data System (ADS)

Tolstorozhev, G. B.; Skornyakov, I. V.; Belkov, M. V.; Shadyro, O. I.; Brinkevich, S. D.; Samovich, S. N.

2012-09-01

We have obtained the Fourier transform IR spectra of solutions of benzaldehyde derivatives having different antiviral activities against a herpes virus. We observe a correlation between the presence of hydrogen bonds in the benzaldehyde molecules and the appearance of antiviral properties in the compounds. For compounds having antiviral activity, we have obtained spectral data suggesting the existence of hydrogen bonds of the type C=OṡṡṡH-O and O-HṡṡṡO in the molecules. When the hydrogen atom in the hydroxyl groups are replaced by a methyl group, no intramolecular hydrogen bonds are formed and the compounds lose their antiviral activity.

Iridium-Catalyzed Hydrogen Transfer Reactions

NASA Astrophysics Data System (ADS)

Saidi, Ourida; Williams, Jonathan M. J.

This chapter describes the application of iridium complexes to catalytic hydrogen transfer reactions. Transfer hydrogenation reactions provide an alternative to direct hydrogenation for the reduction of a range of substrates. A hydrogen donor, typically an alcohol or formic acid, can be used as the source of hydrogen for the reduction of carbonyl compounds, imines, and alkenes. Heteroaromatic compounds and even carbon dioxide have also been reduced by transfer hydrogenation reactions. In the reverse process, the oxidation of alcohols to carbonyl compounds can be achieved by iridium-catalyzed hydrogen transfer reactions, where a ketone or alkene is used as a suitable hydrogen acceptor. The reversible nature of many hydrogen transfer processes has been exploited for the racemization of alcohols, where temporary removal of hydrogen generates an achiral ketone intermediate. In addition, there is a growing body of work where temporary removal of hydrogen provides an opportunity for using alcohols as alkylating agents. In this chemistry, an iridium catalyst "borrows" hydrogen from an alcohol to give an aldehyde or ketone intermediate, which can be transformed into either an imine or alkene under the reaction conditions. Return of the hydrogen from the catalyst provides methodology for the formation of amines or C-C bonds where the only by-product is typically water.

Hydrogen bonding directed self-assembly of small-molecule amphiphiles in water.

PubMed

Xu, Jiang-Fei; Niu, Li-Ya; Chen, Yu-Zhe; Wu, Li-Zhu; Tung, Chen-Ho; Yang, Qing-Zheng

2014-08-01

Compounds comprising one or two quadruply hydrogen bonding units, 2-ureido-4[1H]-pyrimidinone (UPy) and tris(tetraethylene glycol monomethyl ether) moieties, were reported to form highly stable hydrogen-bonded assemblies in water. Compound 1, containing one UPy, assembles into vesicles, and compound 2, containing two UPy units, forms micelles. The aggregates disassemble reversibly when the solution pH is raised to 9.0 or above. The results demonstrate the utility of hydrogen bonding to direct the self-assembly of small-molecule building blocks in aqueous media.

Compound-Specific Isotopic Analysis of Meteoritic Amino Acids as a Tool for Evaluating Potential Formation Pathways

NASA Technical Reports Server (NTRS)

Elsila, Jamie E.; Burton, Aaron S.; Callahan, Michael C.; Charnley, Steven B.; Glavin, Daniel P.; Dworkin, Jason P.

2012-01-01

Measurements of stable hydrogen, carbon, and nitrogen isotopic ratios (delta D, delta C-13, delta N-15) of organic compounds can reveal information about their origin and formation pathways. Several formation mechanisms and environments have been postulated for the amino acids detected in carbonaceous chondrites. As each proposed mechanism utilizes different precursor molecules, the isotopic signatures of the resulting amino acids may point towards the most likely of these proposed pathways. The technique of gas chromatography coupled with mass spectrometry and isotope ratio mass spectrometry provides compound-specific structural and isotopic information from a single splitless injection, enhancing the amount of information gained from small amounts of precious samples such as carbonaceous chondrites. We have applied this technique to measure the compound-specific C, N, and H isotopic ratios of amino acids from seven CM and CR carbonaceous chondrites. We are using these measurements to evaluate predictions of expected isotopic enrichments from potential formation pathways and environments, leading to a better understanding of the origin of these compounds.

Deuterium enrichment by selective photo-induced dissociation of an organic carbonyl compound

DOEpatents

Marling, John B.

1981-01-01

A method for producing a deuterium enriched material by photoinduced dissociation which uses as the working material a gas phase photolytically dissociable organic carbonyl compound containing at least one hydrogen atom bonded to an atom which is adjacent to a carbonyl group and consisting of molecules wherein said hydrogen atom is present as deuterium and molecules wherein said hydrogen atom is present as another isotope of hydrogen. The organic carbonyl compound is subjected to intense infrared radiation at a preselected wavelength to selectively excite and thereby induce dissociation of the deuterium containing species to yield a deuterium enriched stable molecular product. Undissociated carbonyl compound, depleted in deuterium, is preferably redeuterated for reuse.

Discovery of Specific Inhibitors for Intestinal E. coli   β-Glucuronidase through In Silico Virtual Screening

PubMed Central

Cheng, Ta-Chun; Cheng, Kai-Wen; Leu, Yu-Lin; Chuang, Chih-Hung; Huang, Chien-Chaio; Hsieh, Yuan-Chin; Chang, Long-Sen; Cheng, Tian-Lu

2015-01-01

Glucuronidation is a major metabolism process of detoxification for carcinogens, 4-(methylnitrosamino)-1-(3-pyridy)-1-butanone (NNK) and 1,2-dimethylhydrazine (DMH), of reactive oxygen species (ROS). However, intestinal E. coli    β-glucuronidase (eβG) has been considered pivotal to colorectal carcinogenesis. Specific inhibition of eβG may prevent reactivating the glucuronide-carcinogen and protect the intestine from ROS-mediated carcinogenesis. In order to develop specific eβG inhibitors, we found that 59 candidate compounds obtained from the initial virtual screening had high inhibition specificity against eβG but not human βG. In particular, we found that compounds 7145 and 4041 with naphthalenylidene-benzenesulfonamide (NYBS) are highly effective and selective to inhibit eβG activity. Compound 4041  (IC50 = 2.8 μM) shows a higher inhibiting ability than compound 7145  (IC50 = 31.6 μM) against eβG. Furthermore, the molecular docking analysis indicates that compound 4041 has two hydrophobic contacts to residues L361 and I363 in the bacterial loop, but 7145 has one contact to L361. Only compound 4041 can bind to key residue (E413) at active site of eβG via hydrogen-bonding interactions. These novel NYBS-based eβG specific inhibitors may provide as novel candidate compounds, which specifically inhibit eβG to reduce eβG-based carcinogenesis and intestinal injury. PMID:25839056

Discovery of specific inhibitors for intestinal E. coli  β-glucuronidase through in silico virtual screening.

PubMed

Cheng, Ta-Chun; Chuang, Kuo-Hsiang; Roffler, Steve R; Cheng, Kai-Wen; Leu, Yu-Lin; Chuang, Chih-Hung; Huang, Chien-Chaio; Kao, Chien-Han; Hsieh, Yuan-Chin; Chang, Long-Sen; Cheng, Tian-Lu; Chen, Chien-Shu

2015-01-01

Glucuronidation is a major metabolism process of detoxification for carcinogens, 4-(methylnitrosamino)-1-(3-pyridy)-1-butanone (NNK) and 1,2-dimethylhydrazine (DMH), of reactive oxygen species (ROS). However, intestinal E. coli   β-glucuronidase (eβG) has been considered pivotal to colorectal carcinogenesis. Specific inhibition of eβG may prevent reactivating the glucuronide-carcinogen and protect the intestine from ROS-mediated carcinogenesis. In order to develop specific eβG inhibitors, we found that 59 candidate compounds obtained from the initial virtual screening had high inhibition specificity against eβG but not human βG. In particular, we found that compounds 7145 and 4041 with naphthalenylidene-benzenesulfonamide (NYBS) are highly effective and selective to inhibit eβG activity. Compound 4041  (IC50 = 2.8 μM) shows a higher inhibiting ability than compound 7145  (IC50 = 31.6 μM) against eβG. Furthermore, the molecular docking analysis indicates that compound 4041 has two hydrophobic contacts to residues L361 and I363 in the bacterial loop, but 7145 has one contact to L361. Only compound 4041 can bind to key residue (E413) at active site of eβG via hydrogen-bonding interactions. These novel NYBS-based eβG specific inhibitors may provide as novel candidate compounds, which specifically inhibit eβG to reduce eβG-based carcinogenesis and intestinal injury.

Characterization of exhaust emissions from diesel-powered passenger cars with particular reference to unregulated components

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

Lies, K.H.; Postulka, A.; Gring, H.

Besides regulated components VW's research program in the field of characterization of diesel emissions comprises a detailed analysis of the particulates and a comprehensive study of a number of unregulated gaseous compounds. The following chemical compounds and classes of compounds are measured: particulates, traces of metals, major elements, sulfates, sulfur dioxide, hydrogen sulfide, hydrogen cyanide, aldehydes, ammonia, phenols, individual hydrocarbons, and odor (DOAS). The test fleet of this investigation included a number of VW and Audi cars equipped with 4-, and 5-cylinder diesel engines (naturally aspirated and turbocharged). All measurements were performed on a chassis dynamometer in accordance with themore » specification of the known US-test-procedures: Federal Test Procedure, Sulfate Emission Test, Fuel Economy Test. For sampling , in principle, the dilution tunnel technique was used combined with an automatically working collection system. This micro-processor controlled system involves 13 individual sample lines, 8 for gaseous and 5 for particulate components.« less

COMPOUND-SPECIFIC CARBON AND HYDROGEN ISOTOPE ANALYSIS-FIELD EVIDENCE OF MTBE BIOREMEDIATION

EPA Science Inventory

Chemical reactions (including bio- and abiotic degradation) tend to favor molecules with the lighter isotopic species (e.g., 12C, 1H), resulting in enrichment of the heavier isotopic species (13C, D) in the unreacted substrate, referred to as isotopic fractionation. On the other ...

ECO LOGIC INTERNATIONAL GAS-PHASE CHEMICAL REDUCTION PROCESS - THE THERMAL DESORPTION UNIT - APPLICATIONS ANALYSIS REPORT

EPA Science Inventory

ELI ECO Logic International, Inc.'s Thermal Desorption Unit (TDU) is specifically designed for use with Eco Logic's Gas Phase Chemical Reduction Process. The technology uses an externally heated bath of molten tin in a hydrogen atmosphere to desorb hazardous organic compounds fro...

Carbon Isotope Fractionation in Reactions of 1,2-Dibromoethane with FeS and Hydrogen Sulfide

EPA Science Inventory

EDB (1,2-dibromoethane) is frequently detected at sites impacted by leaded gasoline. In reducing environments, EDB is highly susceptible to abiotic degradation. A study was conducted to evaluate the potential of compound-specific isotope analysis (CSIA) in assessing abiotic degr...

In situ catalytic hydrogenation of model compounds and biomass-derived phenolic compounds for bio-oil upgrading

Treesearch

Junfeng Feng; Zhongzhi Yang; Chung-yun Hse; Qiuli Su; Kui Wang; Jianchun Jiang; Junming Xu

2017-01-01

The renewable phenolic compounds produced by directional liquefaction of biomass are a mixture of complete fragments decomposed from native lignin. These compounds are unstable and difficult to use directly as biofuel. Here, we report an efficient in situ catalytic hydrogenation method that can convert phenolic compounds into saturated cyclohexanes. The process has...

Hydrogen storage materials and method of making by dry homogenation

DOEpatents

Jensen, Craig M.; Zidan, Ragaiy A.

2002-01-01

Dry homogenized metal hydrides, in particular aluminum hydride compounds, as a material for reversible hydrogen storage is provided. The reversible hydrogen storage material comprises a dry homogenized material having transition metal catalytic sites on a metal aluminum hydride compound, or mixtures of metal aluminum hydride compounds. A method of making such reversible hydrogen storage materials by dry doping is also provided and comprises the steps of dry homogenizing metal hydrides by mechanical mixing, such as be crushing or ball milling a powder, of a metal aluminum hydride with a transition metal catalyst. In another aspect of the invention, a method of powering a vehicle apparatus with the reversible hydrogen storage material is provided.

2,3-Dihydroxybenzoic acid amides of tetraazaalkanes and tetaaza cycloalkanes

DOEpatents

Weitl, F.L.; Raymond, K.N.

1980-01-01

This disclosure is directed to a compound of the formula given in the patent wherein X is hydrogen or a conventional electron-withdrawing group, particularly --SO[sub 3]H or a salt thereof; n is 2, 3, or 4; m is 2, 3, or 4; and p is 2 or 3. The present compounds are useful as specific sequestering agents for actinide (IV) ions. Also described is a method for the 2,3-dihydroxybenzamidation of azaalkanes. No Drawings

Limitation of tritium outgassing from tritiated solid waste drums

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

Liger, K.; Trabuc, P.; Lefebvre, X.

2015-03-15

In the framework of the development of fusion thermonuclear reactors, tritiated solid waste is foreseen and will have to be managed. The management of tritiated waste implies limitations in terms of activity and tritium degassing. The degassing tritium can be under the form of tritiated hydrogen, tritiated water and, in some specific cases, negligible amount of tritiated volatile organic compound. Hence, considering the major forms of degassing tritium, CEA has developed a mixed-compound dedicated to tritium trapping in drums. Based on several experiments, the foreseen mixed compound is composed of MnO{sub 2}, Ag{sub 2}O, Pt and molecular sieve, the threemore » first species having the ability to convert tritiated hydrogen into tritiated water and the last one acting as a trap for tritiated water. To assess the performance of the trapping mixture, experimental tests were performed at room temperature on tritiated dust composed of beryllium and carbon. It was shown that the metallic oxides mixture used for tritiated hydrogen conversion is efficient and that tritiated water adsorption was limited due to an inefficient regeneration of the molecular sieve prior to its use. Apart from this point, the tritium release from waste was reduced by a factor of 5.5, which can be improved up to 87 if the adsorption step is efficient.« less

Novel chemical scaffolds of the tumor marker AKR1B10 inhibitors discovered by 3D QSAR pharmacophore modeling

PubMed Central

Kumar, Raj; Son, Minky; Bavi, Rohit; Lee, Yuno; Park, Chanin; Arulalapperumal, Venkatesh; Cao, Guang Ping; Kim, Hyong-ha; Suh, Jung-keun; Kim, Yong-seong; Kwon, Yong Jung; Lee, Keun Woo

2015-01-01

Aim: Recent evidence suggests that aldo-keto reductase family 1 B10 (AKR1B10) may be a potential diagnostic or prognostic marker of human tumors, and that AKR1B10 inhibitors offer a promising choice for treatment of many types of human cancers. The aim of this study was to identify novel chemical scaffolds of AKR1B10 inhibitors using in silico approaches. Methods: The 3D QSAR pharmacophore models were generated using HypoGen. A validated pharmacophore model was selected for virtual screening of 4 chemical databases. The best mapped compounds were assessed for their drug-like properties. The binding orientations of the resulting compounds were predicted by molecular docking. Density functional theory calculations were carried out using B3LYP. The stability of the protein-ligand complexes and the final binding modes of the hit compounds were analyzed using 10 ns molecular dynamics (MD) simulations. Results: The best pharmacophore model (Hypo 1) showed the highest correlation coefficient (0.979), lowest total cost (102.89) and least RMSD value (0.59). Hypo 1 consisted of one hydrogen-bond acceptor, one hydrogen-bond donor, one ring aromatic and one hydrophobic feature. This model was validated by Fischer's randomization and 40 test set compounds. Virtual screening of chemical databases and the docking studies resulted in 30 representative compounds. Frontier orbital analysis confirmed that only 3 compounds had sufficiently low energy band gaps. MD simulations revealed the binding modes of the 3 hit compounds: all of them showed a large number of hydrogen bonds and hydrophobic interactions with the active site and specificity pocket residues of AKR1B10. Conclusion: Three compounds with new structural scaffolds have been identified, which have stronger binding affinities for AKR1B10 than known inhibitors. PMID:26051108

The hydrolysis of epoxides catalyzed by inorganic ammonium salts in water: kinetic evidence for hydrogen bond catalysis.

PubMed

Nozière, B; Fache, F; Maxut, A; Fenet, B; Baudouin, A; Fine, L; Ferronato, C

2018-01-17

Naturally-occurring inorganic ammonium ions have been recently reported as efficient catalysts for some organic reactions in water, which contributes to the understanding of the chemistry in some natural environments (soils, seawater, atmospheric aerosols, …) and biological systems, and is also potentially interesting for green chemistry as many of their salts are cheap and non-toxic. In this work, the effect of NH 4 + ions on the hydrolysis of small epoxides in water was studied kinetically. The presence of NH 4 + increased the hydrolysis rate by a factor of 6 to 25 compared to pure water and these catalytic effects were shown not to result from other ions, counter-ions or from acid or base catalysis, general or specific. The small amounts of amino alcohols produced in the reactions were identified as the actual catalysts by obtaining a strong acceleration of the reactions when adding these compounds directly to the epoxides in water. Replacing the amino alcohols by other strong hydrogen-bond donors, such as trifluoroethanol (TFE) or hexafluoroisopropanol (HFIP) gave the same results, demonstrating that the kinetics of these reactions was driven by hydrogen-bond catalysis. Because of the presence of many hydrogen-bond donors in natural environments (for instance amines and hydroxy-containing compounds), hydrogen-bond catalysis is likely to contribute to many reaction rates in these environments.

Low severity coal conversion by ionic hydrogenation: Quarterly report, October--December 1988

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

Maioriello, J.; Larsen, J.W.

1988-12-31

A newly developed reaction system consisting of H/sub 2/O:BF/sub 3//H/sub 2//(CH/sub 3/CN)/sub 2/PtCl/sub 2/ was applied to the ionic hydrogenation of aromatic and functionalized aromatic compounds. Hydrogenations were carried out in this aqueous system at 50/degree/C and 500 psi H/sub 2/. Aryl ethers were hydrogenated and cleaved, yielding deoxygenated, fully saturated compounds as the major products. Reactions of nitrogen-containing aromatic compounds resulted in partial saturation of aromatic rings without cleavage of the C-N bonds. Aromatic and PNA compounds can be fully or partially hydrogenated depending on their structures. Aromatic thiols, sulfides and thiophenes poison the catalyst; the oxidized sulfur formsmore » (sulfonic acids, sulfones) were not reduced and did not poison the catalyst. It was found that certain aromatic compounds were easier to hydrogenate than others. Ionic hydrogenation of Wyodak cola using a H/sub 2/O:BF/sub 3//H/sub 2//(MeCN)/sub 2/PtCl/sub 2/ resulted in no significant increase in THF extractability (5.8--9.6% THF-extractables, wt) over that of the parent coal (4.6--6.7% THF-extractables, wt). Ionic hydrogenation of a demineralized Wyodak coal (1 M aq. citric acid, reflux 1 day) resulted in a slight increase in THF extractability (10.4%) over the untreated parent coal (5.6--5.8%). 4 refs., 1 fig., 1 tab.« less

Hydrogen mobility in the lightest reversible metal hydride, LiBeH 3

DOE PAGES

Mamontov, Eugene; Kolesnikov, Alexander I.; Sampath, Sujatha; ...

2017-11-24

Lithium-beryllium metal hydrides, which are structurally related to their parent compound, BeH 2, offer the highest hydrogen storage capacity by weight among the metal hydrides (15.93 wt. % of hydrogen for LiBeH 3). Challenging synthesis protocols have precluded conclusive determination of their crystallographic structure to date, but here we analyze directly the hydrogen hopping mechanisms in BeH 2 and LiBeH 3 using quasielastic neutron scattering, which is especially sensitive to single-particle dynamics of hydrogen. We find that, unlike its parent compound BeH 2, lithium-beryllium hydride LiBeH 3 exhibits a sharp increase in hydrogen mobility above 265 K, so dramatic thatmore » it can be viewed as melting of hydrogen sublattice. We perform comparative analysis of hydrogen jump mechanisms observed in BeH 2 and LiBeH 3 over a broad temperature range. As microscopic diffusivity of hydrogen is directly related to its macroscopic kinetics, a transition in LiBeH 3 so close to ambient temperature may offer a straightforward and effective mechanism to influence hydrogen uptake and release in this very lightweight hydrogen storage compound.« less

Hydrogen mobility in the lightest reversible metal hydride, LiBeH 3

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

Mamontov, Eugene; Kolesnikov, Alexander I.; Sampath, Sujatha

Lithium-beryllium metal hydrides, which are structurally related to their parent compound, BeH 2, offer the highest hydrogen storage capacity by weight among the metal hydrides (15.93 wt. % of hydrogen for LiBeH 3). Challenging synthesis protocols have precluded conclusive determination of their crystallographic structure to date, but here we analyze directly the hydrogen hopping mechanisms in BeH 2 and LiBeH 3 using quasielastic neutron scattering, which is especially sensitive to single-particle dynamics of hydrogen. We find that, unlike its parent compound BeH 2, lithium-beryllium hydride LiBeH 3 exhibits a sharp increase in hydrogen mobility above 265 K, so dramatic thatmore » it can be viewed as melting of hydrogen sublattice. We perform comparative analysis of hydrogen jump mechanisms observed in BeH 2 and LiBeH 3 over a broad temperature range. As microscopic diffusivity of hydrogen is directly related to its macroscopic kinetics, a transition in LiBeH 3 so close to ambient temperature may offer a straightforward and effective mechanism to influence hydrogen uptake and release in this very lightweight hydrogen storage compound.« less

Estimation of descriptors for hydrogen-bonding compounds from chromatographic and liquid-liquid partition measurements.

PubMed

Lenca, Nicole; Atapattu, Sanka N; Poole, Colin F

2017-12-01

Retention factors obtained by gas chromatography and reversed-phase liquid chromatography on varied columns and partition constants in different liquid-liquid partition systems are used to estimate WSU descriptor values for 36 anilines and N-heterocyclic compounds, 13 amides and related compounds, and 45 phenols and alcohols. These compounds are suitable for use as calibration compounds to characterize separation systems covering the descriptor space E=0.2-3, S=0.4-2.1, A=0-1.5, B=0.1-1.5, L=2.5-10.0 and V=0.5-2.2. Hydrogen-bonding properties are discussed in terms of structure, the possibility of induction effects, intramolecular hydrogen bonding and steric factors for anilines, amides, phenols and alcohols. The relationship between these parameters and observed descriptor values are difficult to predict from structure but facilitate improving the general occupancy of the descriptor space by creating incremental changes in hydrogen-bonding properties. It is verified that the compounds included in this study can be merged with an existing database of compounds recommended for characterizing separation systems. Copyright © 2017 Elsevier B.V. All rights reserved.

Specific aquaporins facilitate the diffusion of hydrogen peroxide across membranes.

PubMed

Bienert, Gerd P; Møller, Anders L B; Kristiansen, Kim A; Schulz, Alexander; Møller, Ian M; Schjoerring, Jan K; Jahn, Thomas P

2007-01-12

The metabolism of aerobic organisms continuously produces reactive oxygen species. Although potentially toxic, these compounds also function in signaling. One important feature of signaling compounds is their ability to move between different compartments, e.g. to cross membranes. Here we present evidence that aquaporins can channel hydrogen peroxide (H2O2). Twenty-four aquaporins from plants and mammals were screened in five yeast strains differing in sensitivity toward oxidative stress. Expression of human AQP8 and plant Arabidopsis TIP1;1 and TIP1;2 in yeast decreased growth and survival in the presence of H2O2. Further evidence for aquaporin-mediated H2O2 diffusion was obtained by a fluorescence assay with intact yeast cells using an intracellular reactive oxygen species-sensitive fluorescent dye. Application of silver ions (Ag+), which block aquaporin-mediated water diffusion in a fast kinetics swelling assay, also reversed both the aquaporin-dependent growth repression and the H2O2-induced fluorescence. Our results present the first molecular genetic evidence for the diffusion of H2O2 through specific members of the aquaporin family.

On the structural and thermodynamic properties of the ?-hydrogen (?, Ce, Nd and Sm) systems

NASA Astrophysics Data System (ADS)

Blazina, Z.; Drasner, A.

1998-06-01

The 0953-8984/10/22/006/img3 (0953-8984/10/22/006/img4, Ce, Nd and Sm) intermetallic compounds were prepared and studied by means of x-ray powder diffraction. All compounds are single phase and exhibit the same hexagonal symmetry (0953-8984/10/22/006/img5 type; space group 0953-8984/10/22/006/img6) as do their prototype 0953-8984/10/22/006/img7 binaries. The interaction with hydrogen was also studied. It was found that all ternary intermetallics react readily and reversibly with hydrogen to form hydrides with high hydrogen contents of up to four hydrogen atoms per alloy formula unit. The pressure composition desorption isotherms were measured. The entropy, the enthalpy and the Gibbs free energy of formation have been extracted from the equilibrium plateau in the pressure-composition desorption isotherms. The hydrogen capacity and the equilibrium pressure of the 0953-8984/10/22/006/img3-hydrogen systems were compared with the corresponding values for their aluminium analogues and with the values for the 0953-8984/10/22/006/img7-hydrogen systems and briefly discussed. The hydride properties of gallium containing and aluminium containing compounds show great similarities whereby both series of ternary compounds form more stable hydrides and exhibit smaller hydrogen capacities than do the corresponding binaries.

Roles of molecular hydrogen and a hydrogen donor solvent in the cracking of moal model compounds with dispersed catalysts

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

Suzuki, Toshimitsu; Ikenaga, Na-oki; Sakota, Takahiro

1994-12-31

It is of great importance to evaluate quantitative hydrogen transfer process by using coal model compounds with a hydrogen-donor solvent. Cronauer el al. showed that in the cracking of benzyl phenyl ether the hydrogen required to stabilize free radicals comes from a donor solvent or intramolecular rearrangement and not from gaseous hydrogen in the absence of a catalyst. Korobkov et al. and Schlosberg et al. showed that the thermolysis of benzyl phenyl ether and dibenzyl ether were accomplished by intramolecular rearrangements. Yokokawa et al. reported that tetralin retarded the catalyzed hydrocracking of coal model compounds containing C-C and C-O bonds.more » However, few studies dealt with quantitative discussion in the hydrogen transfer process from a hydrogen-donor solvent or molecular hydrogen to free radicals derived from a model compound except a series of studies by Nicole and co-workers. On the other hand, it is well known that the amount of naphthalene produced from tetralin decreases after the liquefaction of coal in tetralin with catalyst as compared to the liquefaction in the absence of catalysts. To account for this, two mechanisms are proposed. One is that the catalyst hydrogenates naphthalene produced from tetralin, and the other is that the catalyst promotes the direct hydrogen transfer from molecular hydrogen to free radicals. The purpose of this work is to elucidate the role of catalyst and tetralin by means of the quantitative treatment of the hydrogen transfer reaction stabilizing thermally decomposed free radicals. Cracking of benzyl phenyl ether (BPE), dibenzyl ether (DBE), 1,2-diphenylethane, and 1,3-diphenylpropane was studied in tetralin in the presence of highly disposed catalyst.« less

Towards the synthesis of prenylated phloroglucinol derivatives: An X-ray crystallographic and DFT study of unexpected reaction products

NASA Astrophysics Data System (ADS)

Akerman, Matthew P.; Mkhize, Zimbili; van Heerden, Fanie R.

2018-07-01

Owing to their bioactivity and prevalence in medicinal plant extracts, prenylated phloroglucinols have garnered significant interest. Towards the synthesis of prenylated phloroglucinol derivatives, 2,4,6-trihydroxy-3-(3-methylbut-2-enyl)acetophenone is required as an intermediate. Herein, this was synthesised by a tandem Claisen-Cope rearrangement reaction on 2,4-bis(methoxymethoxy)-6-(3-methylbut-2-enyloxy)acetophenone and a subsequent hydrolysis to remove protecting groups. This reaction yielded the desired product as well as three by-products. Two of these by-products were isomeric chromane derivatives (2 and 3) and the third was a methoxy derivative (4). These compounds have been studied by single crystal X-ray crystallography and DFT methods. Compound (2) crystallised in the P21/c space group with two hydrogen-bonded molecules in the asymmetric unit (Z = 8). Compound (4) crystallised in the Pbca space group with a single molecule in the asymmetric unit (Z = 8). Both compounds formed extensive supramolecular structures supported by hydrogen bonds in the solid state. Compound (2) forms a simple one-dimensional hydrogen-bonded chain co-linear with the a-axis. Compound (4) forms a two-dimensional supramolecular structure comprising "pentameric" hydrogen-bonded motifs linked by additional H-bonds to form the supramolecular structure. Both structures showed intramolecular hydrogen bonds between the acetyl oxygen and adjacent OH group. DFT simulations were used to probe the relative energies of the molecules and hydrogen bonds. These simulations showed that the intramolecular hydrogen bond has a substantial stabilising effect with an interaction strength of 70.64 kJ mol-1. The formation of the hydrogen-bonded dimer of (2) from which the supramolecular structure is formed has a ΔHassoc constant of -42.32 kJ mol-1, illustrating that the formation of the hydrogen-bonded structure is energetically favourable.

Hydrogen Storage Materials for Mobile and Stationary Applications: Current State of the Art.

PubMed

Lai, Qiwen; Paskevicius, Mark; Sheppard, Drew A; Buckley, Craig E; Thornton, Aaron W; Hill, Matthew R; Gu, Qinfen; Mao, Jianfeng; Huang, Zhenguo; Liu, Hua Kun; Guo, Zaiping; Banerjee, Amitava; Chakraborty, Sudip; Ahuja, Rajeev; Aguey-Zinsou, Kondo-Francois

2015-09-07

One of the limitations to the widespread use of hydrogen as an energy carrier is its storage in a safe and compact form. Herein, recent developments in effective high-capacity hydrogen storage materials are reviewed, with a special emphasis on light compounds, including those based on organic porous structures, boron, nitrogen, and aluminum. These elements and their related compounds hold the promise of high, reversible, and practical hydrogen storage capacity for mobile applications, including vehicles and portable power equipment, but also for the large scale and distributed storage of energy for stationary applications. Current understanding of the fundamental principles that govern the interaction of hydrogen with these light compounds is summarized, as well as basic strategies to meet practical targets of hydrogen uptake and release. The limitation of these strategies and current understanding is also discussed and new directions proposed. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effects of hydrogen bond on the melting point of azole explosives

NASA Astrophysics Data System (ADS)

Wang, Jian-Hua; Shen, Chen; Liu, Yu-Cun; Luo, Jin; Duan, Yingjie

2018-07-01

Melting point is an important index to determine whether an explosive can be a melt cast carrier. In this study, the relationship among the molecular structure, crystal structure, and melting point of explosives was investigated by using nitroazole compounds. Hydrogen bonds influence crystal packing modes in chemically understandable ways. Hydrogen bonds also affect the changes in entropy and enthalpy in balancing melting process. Hence, different types of hydrogen bonds in explosive crystal structures were compared when the relationship between the molecular structure and the melting point of nitroazole explosives were analyzed. The effects of methyl and amino groups on intermolecular hydrogen bonds were also compared. Results revealed that the methyl and amino groups connected on the N(1) of the heterocyclic compound can reduce the melting point of azole explosive. This finding is possible because methyl and amino groups destroy the intermolecular hydrogen bond of the heterocyclic compound.

Porous Materials for Hydrolytic Dehydrogenation of Ammonia Borane

PubMed Central

Umegaki, Tetsuo; Xu, Qiang; Kojima, Yoshiyuki

2015-01-01

Hydrogen storage is still one of the most significant issues hindering the development of a “hydrogen energy economy”. Ammonia borane is notable for its high hydrogen densities. For the material, one of the main challenges is to release efficiently the maximum amount of the stored hydrogen. Hydrolysis reaction is a promising process by which hydrogen can be easily generated from this compound. High purity hydrogen from this compound can be evolved in the presence of solid acid or metal based catalyst. The reaction performance depends on the morphology and/or structure of these materials. In this review, we survey the research on nanostructured materials, especially porous materials for hydrogen generation from hydrolysis of ammonia borane. PMID:28793453

Probing the human estrogen receptor-α binding requirements for phenolic mono- and di-hydroxyl compounds: A combined synthesis, binding and docking study

PubMed Central

McCullough, Christopher; Neumann, Terrence S.; Gone, Jayapal Reddy; He, Zhengjie; Herrild, Christian; Wondergem, Julie; Pandey, Rajesh K.; Donaldson, William A.; Sem, Daniel S.

2014-01-01

Various estrogen analogs were synthesized and tested for binding to human ERα using a fluorescence polarization displacement assay. Binding affinity and orientation were also predicted using docking calculations. Docking was able to accurately predict relative binding affinity and orientation for estradiol, but only if a tightly bound water molecule bridging Arg394/Glu353 is present. Di-hydroxyl compounds sometimes bind in two orientations, which are flipped in terms of relative positioning of their hydroxyl groups. Di-hydroxyl compounds were predicted to bind with their aliphatic hydroxyl group interacting with His524 in ERα. One nonsteroid-based dihdroxyl compound was 1000-fold specific for ERβ over ERα, and was also 25-fold specific for agonist ERβ versus antagonist activity. Docking predictions suggest this specificity may be due to interaction of the aliphatic hydroxyl with His475 in the agonist form of ERβ, versus with Thr299 in the antagonist form. But, the presence of this aliphatic hydroxyl is not required in all compounds, since mono-hydroxyl (phenolic) compounds bind ERα with high affinity, via hydroxyl hydrogen bonding interactions with the ERα Arg394/Glu353/water triad, and van der Waals interactions with the rest of the molecule. PMID:24315190

Effect of characteristics of compounds on maintenance of an amorphous state in solid dispersion with crospovidone.

PubMed

Shibata, Yusuke; Fujii, Makiko; Kokudai, Makiko; Noda, Shinobu; Okada, Hideko; Kondoh, Masuo; Watanabe, Yoshiteru

2007-06-01

Solid dispersion (SD) of indomethacin with crospovidone (CrosPVP) shows useful characteristics for preparation of dosage forms. This study aimed to determine the types of drugs that could adopt a stable amorphous form in SD. Twenty compounds with various melting points (70-218 degrees C), molecular weights (135-504) and functional groups (amide, amino, carbonyl, hydroxyl, ketone etc.) were prepared in SD with CrosPVP. The CrosPVP SDs were prepared using a mechanical mixing and heating method. Melting point and molecular weight were found to have no influence on the ability of a compound to maintain an amorphous state in SD. All compounds containing hydrogen-bond-donor functional groups existed in an amorphous state in SD for at least 6 months. Infrared spectra suggested an interaction between the functional groups of these compounds and amide carbonyl group of CrosPVP. Compounds without hydrogen-bond-donor groups could not maintain an amorphous state and underwent recrystallization within 1 month. It was suggested that the presence of a hydrogen-bond-donor functional group in a compound is an important factor affecting the stable formation of SD with CrosPVP, which contains a hydrogen-bond acceptor.

Production of hydrogen from biomass by catalytic steam reforming of fast pyrolysis oil

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

Czernik, S.; Wang, D.; Chornet, E.

1998-08-01

Hydrogen is the prototype of the environmentally cleanest fuel of interest for power generation using fuel cells and for transportation. The thermochemical conversion of biomass to hydrogen can be carried out through two distinct strategies: (a) gasification followed by water-gas shift conversion, and (b) catalytic steam reforming of specific fractions derived from fast pyrolysis and aqueous/steam processes of biomass. This paper presents the latter route that begins with fast pyrolysis of biomass to produce bio-oil. This oil (as a whole or its selected fractions) can be converted to hydrogen via catalytic steam reforming followed by a water-gas shift conversion step.more » Such a process has been demonstrated at the bench scale using model compounds, poplar oil aqueous fraction, and the whole pyrolysis oil with commercial Ni-based steam reforming catalysts. Hydrogen yields as high as 85% have been obtained. Catalyst initial activity can be recovered through regeneration cycles by steam or CO{sub 2} gasification of carbonaceous deposits.« less

Laser-induced separation of hydrogen isotopes in the liquid phase

DOEpatents

Freund, Samuel M.; Maier, II, William B.; Beattie, Willard H.; Holland, Redus F.

1980-01-01

Hydrogen isotope separation is achieved by either (a) dissolving a hydrogen-bearing feedstock compound in a liquid solvent, or (b) liquefying a hydrogen-bearing feedstock compound, the liquid phase thus resulting being kept at a temperature at which spectral features of the feedstock relating to a particular hydrogen isotope are resolved, i.e., a clear-cut isotope shift is delineated, irradiating the liquid phase with monochromatic radiation of a wavelength which at least preferentially excites those molecules of the feedstock containing a first hydrogen isotope, inducing photochemical reaction in the excited molecules, and separating the reaction product containing the first isotope from the liquid phase.

Method and System for Hydrogen Evolution and Storage

DOEpatents

Thorn, David L.; Tumas, William; Hay, P. Jeffrey; Schwarz, Daniel E.; Cameron, Thomas M.

2008-10-21

A method and system for storing and evolving hydrogen employ chemical compounds that can be hydrogenated to store hydrogen and dehydrogenated to evolve hydrogen. A catalyst lowers the energy required for storing and evolving hydrogen. The method and system can provide hydrogen for devices that consume hydrogen as fuel.

Process for oxidation of hydrogen halides to elemental halogens

DOEpatents

Lyke, Stephen E.

1992-01-01

An improved process for generating an elemental halogen selected from chlorine, bromine or iodine, from a corresponding hydrogen halide by absorbing a molten salt mixture, which includes sulfur, alkali metals and oxygen with a sulfur to metal molar ratio between 0.9 and 1.1 and includes a dissolved oxygen compound capable of reacting with hydrogen halide to produce elemental halogen, into a porous, relatively inert substrate to produce a substrate-supported salt mixture. Thereafter, the substrate-supported salt mixture is contacted (stage 1) with a hydrogen halide while maintaining the substrate-supported salt mixture during the contacting at an elevated temperature sufficient to sustain a reaction between the oxygen compound and the hydrogen halide to produce a gaseous elemental halogen product. This is followed by purging the substrate-supported salt mixture with steam (stage 2) thereby recovering any unreacted hydrogen halide and additional elemental halogen for recycle to stage 1. The dissolved oxygen compound is regenerated in a high temperature (stage 3) and an optical intermediate temperature stage (stage 4) by contacting the substrate-supported salt mixture with a gas containing oxygen whereby the dissolved oxygen compound in the substrate-supported salt mixture is regenerated by being oxidized to a higher valence state.

Liquid Organic Hydrogen Carriers (LOHCs): Toward a Hydrogen-free Hydrogen Economy.

PubMed

Preuster, Patrick; Papp, Christian; Wasserscheid, Peter

2017-01-17

The need to drastically reduce CO 2 emissions will lead to the transformation of our current, carbon-based energy system to a more sustainable, renewable-based one. In this process, hydrogen will gain increasing importance as secondary energy vector. Energy storage requirements on the TWh scale (to bridge extended times of low wind and sun harvest) and global logistics of renewable energy equivalents will create additional driving forces toward a future hydrogen economy. However, the nature of hydrogen requires dedicated infrastructures, and this has prevented so far the introduction of elemental hydrogen into the energy sector to a large extent. Recent scientific and technological progress in handling hydrogen in chemically bound form as liquid organic hydrogen carrier (LOHC) supports the technological vision that a future hydrogen economy may work without handling large amounts of elemental hydrogen. LOHC systems are composed of pairs of hydrogen-lean and hydrogen-rich organic compounds that store hydrogen by repeated catalytic hydrogenation and dehydrogenation cycles. While hydrogen handling in the form of LOHCs allows for using the existing infrastructure for fuels, it also builds on the existing public confidence in dealing with liquid energy carriers. In contrast to hydrogen storage by hydrogenation of gases, such as CO 2 or N 2 , hydrogen release from LOHC systems produces pure hydrogen after condensation of the high-boiling carrier compounds. This Account highlights the current state-of-the-art in hydrogen storage using LOHC systems. It first introduces fundamental aspects of a future hydrogen economy and derives therefrom requirements for suitable LOHC compounds. Molecular structures that have been successfully applied in the literature are presented, and their property profiles are discussed. Fundamental and applied aspects of the involved hydrogenation and dehydrogenation catalysis are discussed, characteristic differences for the catalytic conversion of pure hydrocarbon and nitrogen-containing LOHC compounds are derived from the literature, and attractive future research directions are highlighted. Finally, applications of the LOHC technology are presented. This part covers stationary energy storage (on-grid and off-grid), hydrogen logistics, and on-board hydrogen production for mobile applications. Technology readiness of these fields is very different. For stationary energy storage systems, the feasibility of the LOHC technology has been recently proven in commercial demonstrators, and cost aspects will decide on their further commercial success. For other highly attractive options, such as, hydrogen delivery to hydrogen filling stations or direct-LOHC-fuel cell applications, significant efforts in fundamental and applied research are still needed and, hopefully, encouraged by this Account.

Method and system for hydrogen evolution and storage

DOEpatents

Thorn, David L.; Tumas, William; Hay, P. Jeffrey; Schwarz, Daniel E.; Cameron, Thomas M.

2012-12-11

A method and system for storing and evolving hydrogen (H.sub.2) employ chemical compounds that can be hydrogenated to store hydrogen and dehydrogenated to evolve hydrogen. A catalyst lowers the energy required for storing and evolving hydrogen. The method and system can provide hydrogen for devices that consume hydrogen as fuel.

Reconstructing hydroclimatic variations using compound-specific hydrogen isotope analysis of biomarkers from a maar lake in the Central Highlands, Vietnam

NASA Astrophysics Data System (ADS)

Doiron, K. E.; Stevens, L. R.; Sauer, P. E.

2017-12-01

Monsoonal variation in Southeast Asia affects a significant portion of the global population, but knowledge regarding response of the monsoon system to changing boundary conditions is limited. The paleoclimatic tool of compound-specific isotope analysis(CSIA) provides the ability to reconstruct past precipitation using a diverse set of biomarkers preserved in the sedimentary record. Limited proxies in tropical southeast Asia and difficult site access have led to a deficit in paleoclimate records. Ia M'He (14°10'45" N, 107°52' E) is a shallow volcanic crater (maar) lake, approximately 57 ha, located in the Central Highlands of Vietnam. Precipitation in the Central Highlands is sensitive to reorganizations of major climatic features, such as the migration of the ITCZ and the coupled Indo-Asian monsoon, ENSO and related shifts in the Pacific Walker Circulation and typhoon frequency. To examine this complex behavior, this pilot study aims to provide a 500-year record of effective moisture inferred from CSIA of hydrogen isotopes on biomarkers. This study highlights the use of hydrogen isotopes of C28 n-alkanoic acid and dominant n-alkane chain lengths of C27 and C29, associated with terrestrial plant leaf waxes, as tracers for precipitation. The hydrogen isotope ratios of the plant wax components provide a proxy for paleo precipitation in a region where rainfall and droughts heavily influence population dynamics and create social discord. The CSIA record is expected to correlate with records from northern Vietnam, the South China Sea and Indonesia, with greater precipitation during the Little Ice Age. The CSIA data of terrestrial plant leaf waxes will be compared with secondary proxies including: diatoms, C/N and biogenic silica.

Infrared Spectroscopy of Deuterated Compounds.

ERIC Educational Resources Information Center

MacCarthy, Patrick

1985-01-01

Background information, procedures used, and typical results obtained are provided for an experiment (based on the potassium bromide pressed-pellet method) involving the infrared spectroscopy of deuterated compounds. Deuteration refers to deuterium-hydrogen exchange at active hydrogen sites in the molecule. (JN)

A Vibrational Spectral Maker for Probing the Hydrogen-Bonding Status of Protonated Asp and Glu Residues

PubMed Central

Nie, Beining; Stutzman, Jerrod; Xie, Aihua

2005-01-01

Hydrogen bonding is a fundamental element in protein structure and function. Breaking a single hydrogen bond may impair the stability of a protein. We report an infrared vibrational spectral marker for probing the hydrogen-bond number for buried, protonated Asp or Glu residues in proteins. Ab initio computational studies were performed on hydrogen-bonding interactions of a COOH group with a variety of side-chain model compounds of polar and charged amino acids in vacuum using density function theory. For hydrogen-bonding interactions with polar side-chain groups, our results show a strong correlation between the C=O stretching frequency and the hydrogen bond number of a COOH group: ∼1759–1776 cm−1 for zero, ∼1733–1749 cm−1 for one, and 1703–1710 cm−1 for two hydrogen bonds. Experimental evidence for this correlation will be discussed. In addition, we show an approximate linear correlation between the C=O stretching frequency and the hydrogen-bond strength. We propose that a two-dimensional infrared spectroscopy, C=O stretching versus O-H stretching, may be employed to identify the specific type of hydrogen-bonding interaction. This vibrational spectral marker for hydrogen-bonding interaction is expected to enhance the power of time-resolved Fourier transform infrared spectroscopy for structural characterization of functionally important intermediates of proteins. PMID:15653739

Nitro-Assisted Brønsted Acid Catalysis: Application to a Challenging Catalytic Azidation.

PubMed

Dryzhakov, Marian; Hellal, Malik; Wolf, Eléna; Falk, Florian C; Moran, Joseph

2015-08-05

A cocatalytic effect of nitro compounds is described for the B(C6F5)3·H2O catalyzed azidation of tertiary aliphatic alcohols, enabling catalyst turnover for the first time and with a broad range of substrates. Kinetic investigations into this surprising effect reveal that nitro compounds induce a switch from first order concentration dependence in Brønsted acid to second order concentration dependence in Brønsted acid and second order dependence in the nitro compounds. Kinetic, electronic, and spectroscopic evidence suggests that higher order hydrogen-bonded aggregates of nitro compounds and acids are the kinetically competent Brønsted acid catalysts. Specific weak H-bond accepting additives may offer a new general approach to accelerating Brønsted acid catalysis in solution.

Method and apparatus for hydrogen production from water

NASA Technical Reports Server (NTRS)

Muradov, Nazim Z. (Inventor)

2012-01-01

A method, apparatuses and chemical compositions are provided for producing high purity hydrogen from water. Metals or alloys capable of reacting with water and producing hydrogen in aqueous solutions at ambient conditions are reacted with one or more inorganic hydrides capable of releasing hydrogen in aqueous solutions at ambient conditions, one or more transition metal compounds are used to catalyze the reaction and, optionally, one or more alkali metal-based compounds. The metal or alloy is preferably aluminum. The inorganic hydride is from a family of complex inorganic hydrides; most preferably, NaBH.sub.4. The transition metal catalyst is from the groups VIII and IB; preferably, Cu and Fe. The alkali metal-based compounds are preferably NaOH, KOH, and the like. Hydrogen generated has a purity of at least 99.99 vol. % (dry basis), and is used without further purification in all types of fuel cells, including the polymer electrolyte membrane (PEM) fuel cell.

Probing hydrogen positions in hydrous compounds: information from parametric neutron powder diffraction studies.

PubMed

Ting, Valeska P; Henry, Paul F; Schmidtmann, Marc; Wilson, Chick C; Weller, Mark T

2012-05-21

We demonstrate the extent to which modern detector technology, coupled with a high flux constant wavelength neutron source, can be used to obtain high quality diffraction data from short data collections, allowing the refinement of the full structures (including hydrogen positions) of hydrous compounds from in situ neutron powder diffraction measurements. The in situ thermodiffractometry and controlled humidity studies reported here reveal that important information on the reorientations of structural water molecules with changing conditions can be easily extracted, providing insight into the effects of hydrogen bonding on bulk physical properties. Using crystalline BaCl2·2H2O as an example system, we analyse the structural changes in the compound and its dehydration intermediates with changing temperature and humidity levels to demonstrate the quality of the dynamic structural information on the hydrogen atoms and associated hydrogen bonding that can be obtained without resorting to sample deuteration.

Bioisostere Identification by Determining the Amino Acid Binding Preferences of Common Chemical Fragments.

PubMed

Sato, Tomohiro; Hashimoto, Noriaki; Honma, Teruki

2017-12-26

To assist in the structural optimization of hit/lead compounds during drug discovery, various computational approaches to identify potentially useful bioisosteric conversions have been reported. Here, the preference of chemical fragments to hydrogen bonds with specific amino acid residues was used to identify potential bioisosteric conversions. We first compiled a data set of chemical fragments frequently occurring in complex structures contained in the Protein Data Bank. We then used a computational approach to determine the amino acids to which these chemical fragments most frequently hydrogen bonded. The results of the frequency analysis were used to hierarchically cluster chemical fragments according to their amino acid preferences. The Euclid distance between amino acid preferences of chemical fragments for hydrogen bonding was then compared to MMP information in the ChEMBL database. To demonstrate the applicability of the approach for compound optimization, the similarity of amino acid preferences was used to identify known bioisosteric conversions of the epidermal growth factor receptor inhibitor gefitinib. The amino acid preference distance successfully detected bioisosteric fragments corresponding to the morpholine ring in gefitinib with a higher ROC score compared to those based on topological similarity of substituents and frequency of MMP in the ChEMBL database.

Multicomponent hollow tubules formed using phytosterol and gamma-oryzanol-based compounds: an understanding of their molecular embrace.

PubMed

Rogers, Michael A; Bot, Arjen; Lam, Ricky Sze Ho; Pedersen, Tor; May, Tim

2010-08-19

The formation kinetics of self-assembling tubules composed of phytosterol:gamma-oryzanol mixtures were investigated at the Canadian Light Source on the mid-IR beamline using synchrotron radiation and Fourier transform infrared spectroscopy (FT-IR). The Avrami model was fitted to the changing hydrogen bonding density occurring at 3450 cm(-1). The nucleation process was found to be highly dependent on the molecular structure of the phytosterol. The nucleation event for cholesterol:gamma-oryzanol was determined to be sporadic whereas 5alpha-cholestan-3beta-ol:gamma-oryzanol and beta-sitosterol:gamma-oryzanol underwent instantaneous nucleation. One-dimensional growth occurred for each phytosterol:gamma-oryzanol mixture and involved the evolution of highly specific intermolecular hydrogen bonds. More detailed studies on the cholesterol:gamma-oryzanol system indicated that the nucleation activation energy, determined from multiple rate constants, obtained using the Avrami model, was at a minimum when the two compounds were at a 1:1 weight ratio. This resulted in drastic differences to the microscopic structures and affected the macroscopic properties such as turbidity. The formation of the phytosterol:gamma-oryzanol complex was due to intermolecular hydrogen bonding, which was in agreement with the infrared spectroscopic evidence.

Hydrogen bonding: part 78. Ab initio molecular orbital study of intra- and intermolecular hydrogen bonding in choline and betaine and their compounds with HF and H 2O

NASA Astrophysics Data System (ADS)

Harmon, K. M.; Avci, G. F.; Madeira, S. L.; Mounts, P. A.; Thiel, A. C.

2001-10-01

We previously prepared several compounds of the zwitterions [(CH3)3NCH2CH2O]0 (deprotonated choline, herein named cholaine) and [(CH3)3NCH2CO2]0 (betaine) and proposed structures based on infrared spectroscopy. We now examine these compounds with use of ab initio molecular orbital methods to further elucidate possible structure. These calculations demonstrate that: (1) cholaine and betaine both have internal CHO hydrogen bonds, and these are retained in some form in all other compounds. (2) Cholaine hydrate and hydrofluoride and betaine hydrofluoride monomers have covalent three-center hydrogen bonds between H2O or HF and negative zwitterion oxygen, and additional CHX hydrogen bonds to H2O oxygen or HF fluorine. (3) Cholaine monohydrate and cholaine hydrofluoride monohydrate form dimers of Ci symmetry which contain planar C2h (H2O·O)2 and (HOH·F)2 clusters. (4) Cholaine hydrofluoride forms head-to-tail dimers bound by intermolecular CHX hydrogen bonds; this arrangement could lead to extended linear structures in the solid state. (5) Betaine hydrofluoride, in contrast, forms a tightly bound discrete dimeric unit in which two molecules join in a head-to-head manner held together by five intermolecular hydrogen bonds and by the mutual proximities of negative fluorides to positive nitrogens.

Lanthanum nickel aluminum alloy

DOEpatents

Gruen, Dieter M.; Mendelsohn, Marshall H.; Dwight, Austin E.

1979-01-01

A ternary intermetallic compound capable of reversible sorption of hydrogen having the chemical formula LaNi.sub.5-x Al.sub.x, where x is in the range of about 0.01 to 1.5 and the method of storing hydrogen using the intermetallic compound.

Mass spectrometric measurement of hydrogen isotope fractionation for the reactions of chloromethane with OH and Cl

NASA Astrophysics Data System (ADS)

Keppler, Frank; Bahlmann, Enno; Greule, Markus; Schöler, Heinz Friedrich; Wittmer, Julian; Zetzsch, Cornelius

2018-05-01

Chloromethane (CH3Cl) is an important provider of chlorine to the stratosphere but detailed knowledge of its budget is missing. Stable isotope analysis is a potentially powerful tool to constrain CH3Cl flux estimates. The largest degree of isotope fractionation is expected to occur for deuterium in CH3Cl in the hydrogen abstraction reactions with its main sink reactant tropospheric OH and its minor sink reactant Cl atoms. We determined the isotope fractionation by stable hydrogen isotope analysis of the fraction of CH3Cl remaining after reaction with hydroxyl and chlorine radicals in a 3.5 m3 Teflon smog chamber at 293 ± 1 K. We measured the stable hydrogen isotope values of the unreacted CH3Cl using compound-specific thermal conversion isotope ratio mass spectrometry. The isotope fractionations of CH3Cl for the reactions with hydroxyl and chlorine radicals were found to be -264±45 and -280±11 ‰, respectively. For comparison, we performed similar experiments using methane (CH4) as the target compound with OH and obtained a fractionation constant of -205±6 ‰ which is in good agreement with values previously reported. The observed large kinetic isotope effects are helpful when employing isotopic analyses of CH3Cl in the atmosphere to improve our knowledge of its atmospheric budget.

Liquid-phase hydrogenation of citral over Pt/SiO{sub 2} catalysts. 2. Hydrogenation of reaction intermediate compounds

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

Singh, U.K.; Sysak, M.N.; Vannice, M.A.

2000-04-01

Liquid-phase hydrogenation of the four principal reaction intermediates formed during citral hydrogenation, i.e., nerol, geraniol, citronellal, and citronellol, was studied at 298 and 373 K under 20 atm H{sub 2} at concentrations of 0.5 to 1.0 M in hexane. A decrease in the initial reaction rate as temperature increased from 298 to 373 K was exhibited during the hydrogenation of all four compounds, just as reported earlier for citral; however, the decrease in rate at 373 K was only one-half for citronellal whereas it was orders of magnitude greater for nerol and geraniol. Furthermore, simultaneous hydrogenation of citronellal and geraniolmore » at 298 K resulted in a continuous decrease in the rate of citronellal disappearance in contrast to the nearly constant rate of disappearance observed during hydrogenation of citronellal alone. Competitive hydrogenation of citral with either geraniol or citronellal showed that geraniol hydrogenation to citronellol is kinetically insignificant during citral hydrogenation at 373 K. The initial activity for hydrogenation of the intermediates at 298 K follows the following trend: geraniol > nerol < citronellol < E-citral, citronellal > Z-citral. Based on the relative hydrogenation rates of the intermediate alone versus its hydrogenation in the presence of other reactants, the relative size of the adsorption equilibrium constants for the various organic compounds appears to be as follows: citral > citronellal > geraniol, nerol > citronellol > 3,7-dimethyloctanol. This study indicates that activation of the C{double_bond}O bond should be performed at higher reaction temperatures to maximize selectivity to the unsaturated alcohols.« less

Electron spin resonance of an irradiated single crystal of potassium hydrogen maleate

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

Iwasaki, Machio; Itoh, Koichi

1963-09-15

Electron spin resonance absorptions of x-irradiated single crystals of potassium hydrogen maleate and potassium deuterium maleate were observed. Both compounds gave the same hyperfine structures, although the slightly sharper line widths were observed for the deuterium exchanged compound.

Hydrogen storage and phase transformations in Mg-Pd nanoparticles

NASA Astrophysics Data System (ADS)

Callini, E.; Pasquini, L.; Rude, L. H.; Nielsen, T. K.; Jensen, T. R.; Bonetti, E.

2010-10-01

Microstructure refinement and synergic coupling among different phases are currently explored strategies to improve the hydrogen storage properties of traditional materials. In this work, we apply a combination of these methods and synthesize Mg-Pd composite nanoparticles by inert gas condensation of Mg vapors followed by vacuum evaporation of Pd clusters. Irreversible formation of the Mg6Pd intermetallic phase takes place upon vacuum annealing, resulting in Mg/Mg6Pd composite nanoparticles. Their hydrogen storage properties are investigated and connected to the undergoing phase transformations by gas-volumetric techniques and in situ synchrotron radiation powder x-ray diffraction. Mg6Pd transforms reversibly into different Mg-Pd intermetallic compounds upon hydrogen absorption, depending on temperature and pressure. In particular, at 573 K and 1 MPa hydrogen pressure, the metal-hydride transition leads to the formation of Mg3Pd and Mg5Pd2 phases. By increasing the pressure to 5 MPa, the Pd-richer MgPd intermetallic is obtained. Upon hydrogen desorption, the Mg6Pd phase is reversibly recovered. These phase transformations result in a specific hydrogen storage capacity associated with Mg-Pd intermetallics, which attain the maximum value of 3.96 wt % for MgPd and influence both the thermodynamics and kinetics of hydrogen sorption in the composite nanoparticles.

Hydrogen absorption and its effect on magnetic properties of Nd2Fe14B

NASA Astrophysics Data System (ADS)

Bezdushnyi, R.; Damianova, R.; Tereshina, I. S.; Pankratov, N. Yu.; Nikitin, S. A.

2018-05-01

Magnetic properties of hydrides of the intermetallic compound Nd2Fe14BHx are investigated in the temperature range covering the Curie temperatures (TC) of the compounds (up to 670 K). The temperature dependencies of magnetization are measured under continuous control of hydrogen content in the investigated samples. The dependencies of Curie and spin-reorientation transition (TSR) temperatures on the hydrogen concentration are studied in detail. The dependence of hydrogen concentration on pressure at a constant temperature (near TC) and on the temperature at various pressures are obtained. We attempted to estimate the contributions of the unit cell volume increase upon hydrogenation and the electronic structure change in the variation of TC of the hydrogenated Nd2Fe14 B .

Thermochemical process for the production of hydrogen using chromium and barium compound

DOEpatents

Bamberger, Carlos E.; Richardson, Donald M.

1977-01-25

Hydrogen is produced by a closed cyclic process involving the reduction and oxidation of chromium compounds by barium hydroxide and the hydrolytic disproportionation of Ba.sub.2 CrO.sub.4 and Ba.sub.3 (CrO.sub.4).sub.2.

Catalysts for coal liquefaction processes

DOEpatents

Garg, Diwakar

1986-01-01

Improved catalysts for catalytic solvent refining or hydroliquefaction of non-anthracitic coal at elevated temperatures under hydrogen pressure in a hydrogen donor solvent comprise a combination of zinc or copper, or a compound thereof, and a Group VI or non-ferrous Group VIII metal, or a compound thereof.

Catalysts for coal liquefaction processes

DOEpatents

Garg, D.

1986-10-14

Improved catalysts for catalytic solvent refining or hydroliquefaction of non-anthracitic coal at elevated temperatures under hydrogen pressure in a hydrogen donor solvent comprise a combination of zinc or copper, or a compound thereof, and a Group VI or non-ferrous Group VIII metal, or a compound thereof.

Improved bio-hydrogen production from glucose by adding a specific methane inhibitor to microbial electrolysis cells with a double anode arrangement.

PubMed

Zhang, Jingnan; Bai, Yanxia; Fan, Yaoting; Hou, Hongwei

2016-10-01

Improved hydrogen production from glucose was achieved by adding a specific methane inhibitor (such as chloroform) to repress the activity of methanogens in a single-chamber microbial electrolysis cells (MECs) with a double anode arrangement. A maximum hydrogen production of 8.4±0.2 mol H2/mol-G (G represents glucose), a hydrogen production rate of 2.39±0.3 m(3) H2/m3/d and a high energy efficiency (relative to the electrical input) of ηE=165±5% had been recorded from 1 g/L glucose at a low dosage of chloroform (5‰, v:v) and an applied voltage of 0.8 V. Almost all of the glucose was removed within 4 h, with 66% of the electrons in intermediates (mainly including acetate and ethanol), and methane gas was not detected in the MECs through 11 batch cycles. The experimental results confirmed that chloroform was an effective methane inhibitor that improved hydrogen production from glucose in the MECs. In addition, the cyclic voltammetry tests demonstrated that the electron transfer in the MECs was mainly due to the biofilm-bound redox compounds rather than soluble electron shuttles. Copyright © 2016 The Society for Biotechnology, Japan. Published by Elsevier B.V. All rights reserved.

Hydrogen assisted cracking and CO2 corrosion behaviors of low-alloy steel with high strength used for armor layer of flexible pipe

NASA Astrophysics Data System (ADS)

Liu, Zhenguang; Gao, Xiuhua; Du, Linxiu; Li, Jianping; Zhou, Xiaowei; Wang, Xiaonan; Wang, Yuxin; Liu, Chuan; Xu, Guoxiang; Misra, R. D. K.

2018-05-01

In this study, hydrogen induced cracking (HIC), sulfide stress corrosion cracking (SSCC) and hydrogen embrittlement (HE) were carried out to study hydrogen assisted cracking behavior (HIC, SSCC and HE) of high strength pipeline steel used for armor layer of flexible pipe in ocean. The CO2 corrosion behavior of designed steel with high strength was studied by using immersion experiment. The experimental results demonstrate that the corrosion resistance of designed steel with tempered martensite to HIC, SSCC and HE is excellent according to specific standards, which contributes to the low concentration of dislocation and vacancies previously formed in cold rolling process. The corrosion mechanism of hydrogen induced cracking of designed steel, which involves in producing process, microstructure and cracking behavior, is proposed. The designed steel with tempered martensite shows excellent corrosion resistance to CO2 corrosion. Cr-rich compound was first formed on the coupon surface exposed to CO2-saturated brine condition and chlorine, one of the corrosion ions in solution, was rich in the inner layer of corrosion products.

The structure and unconventional dihydrogen bonding of a pressure-stabilized hydrogen-rich (NH 3BH 3)(H 2) x(x = 1.5) compound

DOE PAGES

Lin, Yu; Welchman, Evan; Thonhauser, Timo; ...

2017-03-15

Combining X-ray diffraction, Raman spectroscopy, and ab initio simulations we characterize an extremely hydrogen-rich phase with the chemical formula (NH 3BH 3)(H 2) x (x = 1.5). This phase was formed by compressing ammonia borane (AB, NH 3BH 3) in an environment with an excess of molecular hydrogen (H 2). This compound can store a total of 26.8 wt% hydrogen, both as molecular hydrogen and chemically bonded hydrogen in AB, making it one of the most hydrogen-rich solids currently known. The new compound possesses a layered AB structure where additional H 2 molecules reside in channels created through the weavingmore » of AB layers. The unconventional dihydrogen bonding network of the new compound is significantly modified from its parent AB phase and contains H•••H contacts between adjacent AB molecules and between AB and H 2 molecules. H–H can be either a proton donor or a proton acceptor that forms new types of dihydrogen bonding with the host AB molecules, which are depicted as H–H•••H–B or H–H•••H–N, respectively. Furthermore, this study not only demonstrates the strategy and the promise of using pressure for new material synthesis, but also unleashes the power of combining experiments and ab initio calculations for elucidating novel structures and unusual bonding configurations in dense low-Z materials.« less

The structure and unconventional dihydrogen bonding of a pressure-stabilized hydrogen-rich (NH 3BH 3)(H 2) x(x = 1.5) compound

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

Lin, Yu; Welchman, Evan; Thonhauser, Timo

Combining X-ray diffraction, Raman spectroscopy, and ab initio simulations we characterize an extremely hydrogen-rich phase with the chemical formula (NH 3BH 3)(H 2) x (x = 1.5). This phase was formed by compressing ammonia borane (AB, NH 3BH 3) in an environment with an excess of molecular hydrogen (H 2). This compound can store a total of 26.8 wt% hydrogen, both as molecular hydrogen and chemically bonded hydrogen in AB, making it one of the most hydrogen-rich solids currently known. The new compound possesses a layered AB structure where additional H 2 molecules reside in channels created through the weavingmore » of AB layers. The unconventional dihydrogen bonding network of the new compound is significantly modified from its parent AB phase and contains H•••H contacts between adjacent AB molecules and between AB and H 2 molecules. H–H can be either a proton donor or a proton acceptor that forms new types of dihydrogen bonding with the host AB molecules, which are depicted as H–H•••H–B or H–H•••H–N, respectively. Furthermore, this study not only demonstrates the strategy and the promise of using pressure for new material synthesis, but also unleashes the power of combining experiments and ab initio calculations for elucidating novel structures and unusual bonding configurations in dense low-Z materials.« less

Research Update: Photoelectrochemical water splitting and photocatalytic hydrogen production using ferrites (MFe2O4) under visible light irradiation

NASA Astrophysics Data System (ADS)

Dillert, Ralf; Taffa, Dereje H.; Wark, Michael; Bredow, Thomas; Bahnemann, Detlef W.

2015-10-01

The utilization of solar light for the photoelectrochemical and photocatalytic production of molecular hydrogen from water is a scientific and technical challenge. Semiconductors with suitable properties to promote solar-driven water splitting are a desideratum. A hitherto rarely investigated group of semiconductors are ferrites with the empirical formula MFe2O4 and related compounds. This contribution summarizes the published results of the experimental investigations on the photoelectrochemical and photocatalytic properties of these compounds. It will be shown that the potential of this group of compounds in regard to the production of solar hydrogen has not been fully explored yet.

A comparative study between para-aminophenyl and ortho-aminophenyl benzothiazoles using NMR and DFT calculations.

PubMed

Pierens, G K; Venkatachalam, T K; Reutens, D

2014-08-01

Ortho-substituted and para-substituted aminophenyl benzothiazoles were synthesised and characterised using NMR spectroscopy. A comparison of the proton chemical shift values reveals significant differences in the observed chemical shift values for the NH protons indicating the presence of a hydrogen bond in all ortho-substituted compounds as compared to the para compounds. The presence of intramolecular hydrogen bond in the ortho amino substituted aminophenyl benzothiazole forces the molecule to be planar which may be an additional advantage in developing these compounds as Alzheimer's imaging agent because the binding to amyloid fibrils prefers planar compounds. The splitting pattern of the methylene proton next to the amino group also showed significant coupling to the amino proton consistent with the notion of the existence of slow exchange and hydrogen bond in the ortho-substituted compounds. This is further verified by density functional theory calculations which yielded a near planar low energy conformer for all the o-aminophenyl benzothiazoles and displayed a hydrogen bond from the amine proton to the nitrogen of the thiazole ring. A detailed analysis of the (1)H, (13)C and (15)N NMR chemical shifts and density functional theory calculated structures of the compounds are described. Copyright © 2014 John Wiley & Sons, Ltd.

Compound-specific carbon and hydrogen isotope analysis of sub-parts per billion level waterborne petroleum hydrocarbons

USGS Publications Warehouse

Wang, Y.; Huang, Y.; Huckins, J.N.; Petty, J.D.

2004-01-01

Compound-specific carbon and hydrogen isotope analysis (CSCIA and CSHIA) has been increasingly used to study the source, transport, and bioremediation of organic contaminants such as petroleum hydrocarbons. In natural aquatic systems, dissolved contaminants represent the bioavailable fraction that generally is of the greatest toxicological significance. However, determining the isotopic ratios of waterborne hydrophobic contaminants in natural waters is very challenging because of their extremely low concentrations (often at sub-parts ber billion, or even lower). To acquire sufficient quantities of polycyclic aromatic hydrocarbons with 10 ng/L concentration for CSHIA, more than 1000 L of water must be extracted. Conventional liquid/liquid or solid-phase extraction is not suitable for such large volume extractions. We have developed a new approach that is capable of efficiently sampling sub-parts per billion level waterborne petroleum hydrocarbons for CSIA. We use semipermeable membrane devices (SPMDs) to accumulate hydrophobic contaminants from polluted waters and then recover the compounds in the laboratory for CSIA. In this study, we demonstrate, under a variety of experimental conditions (different concentrations, temperatures, and turbulence levels), that SPMD-associated processes do not induce C and H isotopic fractionations. The applicability of SPMD-CSIA technology to natural systems is further demonstrated by determining the ??13C and ??D values of petroleum hydrocarbons present in the Pawtuxet River, RI. Our results show that the combined SPMD-CSIA is an effective tool to investigate the source and fate of hydrophobic contaminants in the aquatic environments.

Peculiar hydrogenation process of Ce2Ni2Ga

NASA Astrophysics Data System (ADS)

Iwasieczko, Wacław; Kaczorowski, Dariusz

2017-02-01

Hydrogenation studies were carried out on the compound Ce2Ni2Ga that was described in the literature as an intermediate valence system. The alloy was found to absorb hydrogen very easily already at room temperature under pressure less than 0.1 MPa forming hydrides Ce2Ni2GaHx with x up 5.9, which are however multiphase and contain CeH2+δ and some other undisclosed phases. Analyses of the X-ray diffraction and magnetic data revealed that decomposition of the parent compound occurs immediately after its exposure to hydrogen. Synthesis under hydrogen pressure of 3 MPa at 470 K resulted in amorphous material with x=7.3. The Ce2Ni2GaHx system was found to exhibit a HDDR (hydrogenation, disproportionation, desorption, recombination) process.

Toward prediction of alkane/water partition coefficients.

PubMed

Toulmin, Anita; Wood, J Matthew; Kenny, Peter W

2008-07-10

Partition coefficients were measured for 47 compounds in the hexadecane/water ( P hxd) and 1-octanol/water ( P oct) systems. Some types of hydrogen bond acceptor presented by these compounds to the partitioning systems are not well represented in the literature of alkane/water partitioning. The difference, DeltalogP, between logP oct and logP hxd is a measure of the hydrogen bonding potential of a molecule and is identified as a target for predictive modeling. Minimized molecular electrostatic potential ( V min) was shown to be an effective predictor of the contribution of hydrogen bond acceptors to DeltalogP. Carbonyl oxygen atoms were found to be stronger hydrogen bond acceptors for their electrostatic potential than heteroaromatic nitrogen or oxygen bound to hypervalent sulfur or nitrogen. Values of V min calculated for hydrogen-bonded complexes were used to explore polarization effects. Predicted logP hxd and DeltalogP were shown to be more effective than logP oct for modeling brain penetration for a data set of 18 compounds.

Combination moisture and hydrogen getter

DOEpatents

Harrah, L.A.; Mead, K.E.; Smith, H.M.

1983-09-20

A combination moisture and hydrogen getter comprises (a) a moisture getter comprising a readily oxidizable metal; and (b) a hydrogen getter comprising (1) a solid acetylenic compound and (2) a hydrogenation catalyst. A method of scavenging moisture from a closed container uses the combination moisture and hydrogen getter to irreversibly chemically reduce the moisture and chemically bind the resultant hydrogen.

Combination moisture and hydrogen getter

DOEpatents

Harrah, Larry A.; Mead, Keith E.; Smith, Henry M.

1983-01-01

A combination moisture and hydrogen getter comprises (a) a moisture getter comprising a readily oxidizable metal; and (b) a hydrogen getter comprising (i) a solid acetylenic compound and (ii) a hydrogenation catalyst. A method of scavenging moisture from a closed container uses the combination moisture and hydrogen getter to irreversibly chemically reduce the moisture and chemically bind the resultant hydrogen.

Combination moisture and hydrogen getter

DOEpatents

Not Available

1982-04-29

A combination moisture and hydrogen getter comprises (a) a moisture getter comprising a readily oxidizable metal; and (b) a hydrogen getter comprising (i) a solid acetylenic compound and (ii) a hydrogenation catalyst. A method of scavenging moisture from a closed container uses the combination moisture and hydrogen getter to irreversibly chemically reduce the moisture and chemically bind the reusltant hydrogen.

Method of gettering hydrogen under conditions of low pressure

DOEpatents

Mendelsohn, M.H.; Gruen, D.M.

1983-08-09

A ternary intermetallic compound having the formula Zr(V[sub 1[minus]x]Cr[sub x])[sub 2] where x is in the range of 0.01 to 0.90 is capable of reversibly sorbing hydrogen at temperatures ranging from room temperature to 200 C, at pressures down to 10[sup [minus]6] Torr. The compound is suitable for use as a hydrogen getter in low pressure, high temperature applications such as magnetic confinement fusion devices. 3 figs.

Preparation of Chemicals and Bulk Drug Substances for the U.S. Army Drug Development Program

DTIC Science & Technology

1997-12-01

alkylation method. Reduction of the 8-nitro group in compound 3 was accomplished readily by hydrogenation over Raney nickel catalyst . Pure 8...1 with fuming nitric acid in concentrated sulfuric acid gave the 4- nitropyridine 2. The reduction of compound 2 by hydrogenation over Raney nickel catalyst as...The isomers were separated by fractional crystallization and the pure 3-nitropyridine 5 was hydrogenated over Raney nickel catalyst to give

Progress in donor assisted coal liquefaction: Hydroaromatic compound formation

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

Kottenstette, R.J.; Stephens, H.P.

1993-12-31

The role of hydrogen donor compounds in coal liquefaction has been extensively investigated since the mid 1960`s using model compounds and process derived hydrogen donor solvents. Our recent research and that of other investigators have shown that two model compounds in particular have great efficacy in solvating low rank coals. 1,2,3,10b tetrahydrofluoranthene (H{sub 4}Fl) and 1,2,3,6,7,8 hexahydropyrene (H{sub 6}Py) have been used to dissolve Wyodak coal to > 95% soluble material as measured by tetrahydrofuran (THF). Although these hydrogen donors are very effective, they may not be found in any significant concentrations in actual liquefaction process recycle solvents. Therefore, studiesmore » with process derived recycle materials are necessary to understand donor solvent chemistry. The objective of this paper is to present results of solvent hydrogenation experiments using heavy distillate solvents produced during testing at the Wilsonville Advanced Coal Liquefaction Test Facility. We evaluated the impact of hydrogenation conditions upon hydrogen donor formation in process derived distillates and compared these process derived solvents with the highly effective H{sub 4}Fl and H{sub 6}Py donors in coal liquefaction tests. This paper presents data on reaction conditions used for distillate hydrotreating and subsequent coal liquefaction, with an aim toward understanding the relationship between reaction conditions and donor solvent quality in recycle distillates.« less

Magnetic Silica-Supported Ruthenium Nanoparticles: An Efficient Catalyst for Transfer Hydrogenation of Carbonyl Compounds

EPA Science Inventory

One-pot synthesis of ruthenium nanoparticles on magnetic silica is described which involve the in situ generation of magnetic silica (Fe3O4@ SiO2) and ruthenium nano particles immobilization; the hydration of nitriles and transfer hydrogenation of carbonyl compounds occurs in hi...

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.

Isotopic disproportionation during hydrogen isotopic analysis of nitrogen-bearing organic compounds

USGS Publications Warehouse

Nair, Sreejesh; Geilmann, Heike; Coplen, Tyler B.; Qi, Haiping; Gehre, Matthias; Schimmelmann, Arndt; Brand, Willi A.

2015-01-01

Rationale High-precision hydrogen isotope ratio analysis of nitrogen-bearing organic materials using high-temperature conversion (HTC) techniques has proven troublesome in the past. Formation of reaction products other than molecular hydrogen (H2) has been suspected as a possible cause of incomplete H2 yield and hydrogen isotopic fractionation. Methods The classical HTC reactor setup and a modified version including elemental chromium, both operated at temperatures in excess of 1400 °C, have been compared using a selection of nitrogen-bearing organic compounds, including caffeine. A focus of the experiments was to avoid or suppress hydrogen cyanide (HCN) formation and to reach quantitative H2 yields. The technique also was optimized to provide acceptable sample throughput. Results The classical HTC reaction of a number of selected compounds exhibited H2 yields from 60 to 90 %. Yields close to 100 % were measured for the experiments with the chromium-enhanced reactor. The δ2H values also were substantially different between the two types of experiments. For the majority of the compounds studied, a highly significant relationship was observed between the amount of missing H2and the number of nitrogen atoms in the molecules, suggesting the pyrolytic formation of HCN as a byproduct. A similar linear relationship was found between the amount of missing H2 and the observed hydrogen isotopic result, reflecting isotopic fractionation. Conclusions The classical HTC technique to produce H2 from organic materials using high temperatures in the presence of glassy carbon is not suitable for nitrogen-bearing compounds. Adding chromium to the reaction zone improves the yield to 100 % in most cases. The initial formation of HCN is accompanied by a strong hydrogen isotope effect, with the observed hydrogen isotope results on H2 being substantially shifted to more negative δ2H values. The reaction can be understood as an initial disproportionation leading to H2 and HCN with the HCN-hydrogen systematically enriched in 2H by more than 50 ‰. In the reaction of HCN with chromium, H2 and chromium-containing solid residues are formed quantitatively.

Isoelectronic Manganese and Iron Hydrogenation/Dehydrogenation Catalysts: Similarities and Divergences.

PubMed

Gorgas, Nikolaus; Kirchner, Karl

2018-06-19

Sustainable processes that utilize nontoxic, readily available, and inexpensive starting materials for organic synthesis constitute a major objective in modern chemical research. In this context, it is highly important to perform reactions under catalytic conditions and to replace precious metal catalysts by earth-abundant nonprecious metal catalysts. In particular, iron and manganese are promising candidates, as these are among the most abundant metals in the earth's crust, are inexpensive, and exhibit a low environmental impact. As far as chemical processes are concerned, hydrogenations and acceptorless alcohol dehydrogenation (AAD), sometimes in conjunction with hydrogen autotransfer reactions, are becoming important areas of research. While the first is a very important synthetic process representing a highly atom-efficient and clean methodology, AAD is an oxidant-free, environmentally benign reaction where carbonyl compounds together with dihydrogen as a valuable product and/or reactant (autotransfer) and water are formed. Carbonyl compounds, typically generated in situ, can be converted into other useful organic materials such as amines, imines, or heterocycles. In 2016 several groups, including ours, discovered for the first time the potential of hydride biscarbonyl Mn(I) complexes bearing strongly bound PNP pincer ligands or related tridentate ligands as highly effective and versatile catalysts for hydrogenation, transfer hydrogenation, and dehydrogenation reactions. These complexes are isoelectronic analogues of the respective hydride monocarbonyl Fe(II) PNP compounds and display similar reactivities but also quite divergent behavior depending on the coligands. Moreover, manganese compounds show improved long-term stability and high robustness toward harsh reaction conditions. In light of these recent achievements, this Account contrasts Mn(I) and Fe(II) PNP pincer catalysts, highlighting specific features that are connected to particular structural and electronic properties. It also addresses opportunities and restrictions in their catalytic applications. Apart from classical hydrogenations, it also covers the most recent developments of these catalysts for AAD resulting in the synthesis of complex organic molecules such as heterocycles via multicomponent reactions. The ambivalent hydrogen-based redox chemistry provides access to a variety of synthetically valuable reductive and oxidative coupling reactions. Hence, these catalysts cover a broad scope of catalytic applications and exhibit activities and productivities that are becoming competitive with those of well-established precious metal catalysts. The knowledge about the nature and characteristics of active Mn(I)- and Fe(II)-based systems paves the way for conceptually and mechanistically well-founded research, which might lead to further developments and the discovery of novel catalysts extending the current scope and limitations of reactivity. It underlines that base metal catalysts are beginning to challenge precious metal catalysts and contributes to the further advancement of waste-free sustainable base metal catalysis.

Multi-element compound specific stable isotope analysis of volatile organic compounds at trace levels in groundwater samples

NASA Astrophysics Data System (ADS)

Herrero-Martín, Sara; Nijenhuis, Ivonne; Schmidt, Marie; Wolfram, Diana; Richnow, Hans. H.; Gehre, Matthias

2013-04-01

Groundwater pollution remains one of the major environmental and health concerns. A thorough understanding of sources, sinks and transformation processes of groundwater contaminants is needed to improve risk management evaluation, and to design efficient remediation and water treatment strategies. Isotopic tools provide unique information for an in-depth understanding of the fate of organic chemicals in the environment. During the last decades compound specific isotope analysis (CSIA) of complex mixtures, using gas chromatography-isotope ratio mass spectrometry (GC-IRMS), has gained popularity for the characterization and risk assessment of hazardous waste sites and for isotope forensics of organic contaminants. Multi-element isotope fingerprinting of organic substances provides a more robust framework for interpretation than the isotope analysis of only one element. One major challenge for application of CSIA is the analysis of trace levels of organic compounds in environmental matrices. It is necessary to inject 1 nmol carbon or 8 nmol hydrogen on column, to obtain an accurate and precise measurement of the isotope ratios, which is between two and three orders of magnitude larger than the amount of compound needed for conventional analysis of compound concentrations. Therefore, efficient extraction and pre-concentration techniques have to be integrated with GC-IRMS. Further research is urgently needed in this field, to evaluate the potential of novel and environmental-friendly sample pre-treatment techniques for CSIA to lower the detection limits and extending environmental applications. In this study, the novel coupling of a headspace autosampler (HS) with a programmed temperature vaporizer (PTV), allowing large volume injection of headspace samples, is proposed to improve the sensitivity of CSIA. This automatic, fast and solvent free strategy provides a significant increase on the sensitivity of GC-based methods maintaining the simple headspace instrumentation. The method was developed for the multi-element isotope analysis (carbon and hydrogen) of priority volatile organic groundwater pollutants (methyl tert-butyl ether (MTBE), benzene, toluene, ethylbenzene and o-xylene (BTEX)), and for carbon isotope analysis of chlorinated benzenes and ethenes. The extraction and injection conditions were optimized in terms of maximum sensitivity and minimum isotope effects. During the injection of the headspace sample, the liner is maintained at a low temperature, such that the compounds are retained in a hydrophobic insert packing while the water vapor is eliminated through the split line. With the optimized conditions, it was possible to inject up to 5mL headspace sample with no significant carbon or hydrogen isotopic effects except for the most hydrophobic substance (MTBE), which was subject to a small and reproducible isotope fractionation for hydrogen. The increment on method sensitivity was at least 20 fold in comparison with conventional static headspace analysis. The environmental applicability of the HS-PTV-GC-IRMS method was evaluated by the analysis of groundwater samples from different contaminated field sites, containing BTEX and chlorinated volatile organic contaminants in the low µg/L range. The results obtained demonstrate that this pre-concentration technique is highly promising to enhance the limits of detection of current CSIA methods and broaden its possibilities.

Development and Performance of the Oxygen Sensor in the CSA-CP Aboard the International Space Station

NASA Technical Reports Server (NTRS)

Limero, Thomas; Beck, Steve; James, John T.

2004-01-01

A combustion products analyzer (CPA) was built for use on Shuttle in response to several thermodegradation incidents that had occurred during early flights. The CPA contained sensors that measured carbon monoxide, hydrogen chloride, hydrogen cyanide, and hydrogen fluoride. These marker compounds, monitored by the CPA, were selected based upon the likely products to be released in a spacecraft fire. When the Toxicology Laboratory group at Johnson Space Center (JSC) began to assess the air quality monitoring needs for the International Space Station (ISS), the CPA was the starting point for design of an instrument to monitor the atmosphere following a thermodegradation event. The final product was significantly different from the CPA and was named the compound specific analyzer-combustion products (CSA-CP). The major change from the CPA that will be the focus of this paper was the replacement of an unreliable hydrogen fluoride (HF) sensor with an oxygen sensor. A reliable HF sensor was not commercially available, but as the toxicology group reviewed the overall monitoring strategy for ISS, it appeared that a portable oxygen sensor to backup the major constituent analyzer was needed. Therefore, an oxygen sensor replaced the HF sensor in the new instrument. This paper will describe the development, deployment, and performance of the CSA-CP oxygen sensor on both Shuttle and ISS. Also, data for CSA-CP oxygen sensor accuracy at nominal and reduced pressures will be presented.

Selective gas-chromatographic detection using an ion-selective electrode-II Selective detection of fluorine compounds.

PubMed

Kojima, T; Ichise, M; Seo, Y

1972-04-01

Components in samples are separated on a gas chromatography column using hydrogen as carrier gas. The individual components from the column are passed through a platinum tube heated at 1000 degrees , where they undergo hydrogenolysis, and fluorine compounds are converted into hydrogen fluoride. The hydrogen fluoride is dissolved in a slow stream of an absorption solution, and the fluoride ion concentration in the resulting solution is monitored in a flow-cell with a fluoride ion electrode. The potentiometric output of the cell is converted into a signal, which is proportional to the concentration of fluoride ion, by an antilogarithmic converter, and recorded. The response of the detector to fluorine compounds was about 10,000 times that to an equal quantity of other organic compounds, and 5 x 10(-11) mole of fluorobenzene could be detected.

Research Update: Photoelectrochemical water splitting and photocatalytic hydrogen production using ferrites (MFe{sub 2}O{sub 4}) under visible light irradiation

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

Dillert, Ralf; Laboratorium für Nano- und Quantenengineering, Gottfried Wilhelm Leibniz Universität Hannover, Schneiderberg 39, 30167 Hannover; Taffa, Dereje H.

2015-10-01

The utilization of solar light for the photoelectrochemical and photocatalytic production of molecular hydrogen from water is a scientific and technical challenge. Semiconductors with suitable properties to promote solar-driven water splitting are a desideratum. A hitherto rarely investigated group of semiconductors are ferrites with the empirical formula MFe{sub 2}O{sub 4} and related compounds. This contribution summarizes the published results of the experimental investigations on the photoelectrochemical and photocatalytic properties of these compounds. It will be shown that the potential of this group of compounds in regard to the production of solar hydrogen has not been fully explored yet.

THE EXCHANGE OF DEUTERIUM WITH METHANOL OVER RANEY NICKEL CATALYST AND THE EFFECT OF CERTAIN NITRO COMPOUNDS UPON THE EXCHANGE

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

Smith, H.A.; Stewart, B.B.

Deuterium gas exchanges slowly with liquid methanol over Raney nickel catalyst at 35 deg . The reaction is zero order with respect to deuterium pressure and has a low activation energy. The influences of catalyst weight, catalyst treatment, and of the presence of certain nitro compounds were studied. Since active Raney nickel can liberate hydrogen directly, a method for determining the origin of hydrogen which undergoes exchange with the deuterium gas was developed. It was shown that the exchanged hydrogen does originate from the hydroxyl hydrogen of methanol. The results are discussed in the light of the mechanism of catalyticmore » exchange and catalytic hydrogenation reactions. (auth)« less

Regio- and chemoselective reduction of nitroarenes and carbonyl compounds over recyclable magnetic ferrite-nickel nanoparticles (Fe(3)O(4)-Ni) by using glycerol as a hydrogen source.

PubMed

Gawande, Manoj B; Rathi, Anuj K; Branco, Paula S; Nogueira, Isabel D; Velhinho, Alexandre; Shrikhande, Janhavi J; Indulkar, Utkarsha U; Jayaram, Radha V; Ghumman, C Amjad A; Bundaleski, Nenad; Teodoro, Orlando M N D

2012-10-01

Reduction by magnetic nano-Fe(3)O(4)-Ni: a facile, simple and environmentally friendly hydrogen-transfer reaction that takes place over recyclable ferrite-nickel magnetic nanoparticles (Fe(3)O(4)-Ni) by using glycerol as hydrogen source allows aromatic amines and alcohols to be synthesized from the precursor nitroarenes and carbonyl compounds. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Novel chemoselective hydrogenation of aromatic nitro compounds over ferric hydroxide supported nanocluster gold in the presence of CO and H2O.

PubMed

Liu, Lequan; Qiao, Botao; Chen, Zhengjian; Zhang, Juan; Deng, Youquan

2009-02-14

Chemoselective hydrogenation of aromatic nitro compounds were first efficiently achieved over Au/Fe(OH)(x) at 100-120 degrees C for 1.5-6 h (depending on different substrates) in the presence of CO and H(2)O.

Hydrogen Release Compound (HRC®) Barrier Application At The North Of Basin F Site, Rocky Mountain Arsenal; Innovative Technology Evaluation Report

EPA Science Inventory

This Innovative Technology Evaluation Report documents the results of a demonstration of the hydrogen release compound (HRC^®) barrier technology developed by Regenesis Bioremediation Products, Inc., of San Clemente, California. HRC^® is a proprietary, food-q...

ULTRAFAST CHEMISTRY: Using Time-Resolved Vibrational Spectroscopy for Interrogation of Structural Dynamics

NASA Astrophysics Data System (ADS)

Nibbering, Erik T. J.; Fidder, Henk; Pines, Ehud

2005-05-01

Time-resolved infrared (IR) and Raman spectroscopy elucidates molecular structure evolution during ultrafast chemical reactions. Following vibrational marker modes in real time provides direct insight into the structural dynamics, as is evidenced in studies on intramolecular hydrogen transfer, bimolecular proton transfer, electron transfer, hydrogen bonding during solvation dynamics, bond fission in organometallic compounds and heme proteins, cis-trans isomerization in retinal proteins, and transformations in photochromic switch pairs. Femtosecond IR spectroscopy monitors the site-specific interactions in hydrogen bonds. Conversion between excited electronic states can be followed for intramolecular electron transfer by inspection of the fingerprint IR- or Raman-active vibrations in conjunction with quantum chemical calculations. Excess internal vibrational energy, generated either by optical excitation or by internal conversion from the electronic excited state to the ground state, is observable through transient frequency shifts of IR-active vibrations and through nonequilibrium populations as deduced by Raman resonances.

Catalytic homogeneous hydrogenation of compounds containing X --> O semipolar bonds (X = N, S, P) with para-hydrogen as a promising route for preparation of para-water.

PubMed

Ustynyuk, Yuri A; Gavrikov, Alexei V; Sergeyev, Nikolay M

2006-11-28

The quantum-chemical simulation (DFT, PBE, TZ2p basis set) of the mechanism of catalytic hydrogenation of compounds containing R(n)X --> O semipolar bonds (R(n)X = N(2), Me(2)S, C(5)H(5)N, Ph(3)P) on the Wilkinson catalyst (Ph(3)P)(3)RhCl with para-hydrogen showed that this process proceeds with retention of proton nuclear spin correlation, which enables a principal possibility to synthesize para-H(2)O, i.e. the nuclear spin isomer of water with antiparallel proton spins, using this route.

Di- and tri-benzotriazole substituted tri-hydroxybenzenes

DOEpatents

Vogl, O.; Li, S.

1983-10-06

Ultraviolet light stabilizing compounds of the formula (phenyl) R/sub 1/, R/sub 2/(OH)/sub 3/R/sub 3/, are described, wherein R/sub 1/, R/sub 2/, and R/sub 3/ are hydrogen or 2H-benzotriazole-2-yl groups and wherein no more than one of R/sub 1/, R/sub 2/, and R/sub 3/ is hydrogen, and organic compositions susceptible to ultraviolet light degradation containing these compounds, and method for selectively producing the compounds.

Validation of GC-IRMS techniques for δ13C and δ2H CSIA of organophosphorus compounds and their potential for studying the mode of hydrolysis in the environment.

PubMed

Wu, Langping; Kümmel, Steffen; Richnow, Hans H

2017-04-01

Compound-specific stable isotope analysis (CSIA) is among the most promising tools for studying the fate of organic pollutants in the environment. However, the feasibility of multidimensional CSIA was limited by the availability of a robust method for precise isotope analysis of heteroatom-bearing organic compounds. We developed a method for δ 13 C and δ 2 H analysis of eight organophosphorus compounds (OPs) with different chemical properties. In particular, we aimed to compare high-temperature conversion (HTC) and chromium-based HTC (Cr/HTC) units to explore the limitations of hydrogen isotope analysis of heteroatom-bearing compounds. Analysis of the amount dependency of the isotope values (linearity analysis) of OPs indicated that the formation of HCl was a significant isotope fractionation process leading to inaccurate δ 2 H analysis in HTC. In the case of nonchlorinated OPs, by-product formation of HCN, H 2 S, or PH 3 in HTC was observed but did not affect the dynamic range of reproducible isotope values above the limit of detection. No hydrogen-containing by-products were found in the Cr/HTC process by use of ion trap mass spectrometry analysis. The accuracy of gas chromatography - isotope ratio mass spectrometry was validated in comparison with elemental analyzer - isotope ratio mass spectrometry. Dual-isotope fractionation yielded Λ values of 0 ± 0 at pH 7, 7 ± 1 at pH 9, and 30 ± 6 at pH 12, indicating the potential of 2D CSIA to characterize the hydrolysis mechanisms of OPs. This is the first report on the combination of δ 2 H and δ 13 C isotope analysis of OPs, and this is the first study providing a systematic evaluation of HTC and Cr/HTC for hydrogen isotope analysis using OPs as target compounds. Graphical Abstract Comparison of δ 2 H measurement of non-chlorinated and chlorinated OPs via GC-Cr/HTC-IRMS and GC-HTC-IRMS system.

Ferrocenylaniline based amide analogs of methoxybenzoic acids: Synthesis, structural characterization and butyrylcholinesterase (BChE) inhibition studies

NASA Astrophysics Data System (ADS)

Altaf, Ataf Ali; Kausar, Samia; Hamayun, Muhammad; Lal, Bhajan; Tahir, Muhammad Nawaz; Badshah, Amin

2017-10-01

Three new ferrocene based amides were synthesized with slight structural difference. The general formula of the amides is C5H5FeC5H4C6H4NHCOC6H4(OCH3). The synthesized compounds were characterized by instrumental techniques like elemental analysis, FTIR and NMR spectroscopy. Structure of the two compounds was also studied by single crystal X-rays diffraction analysis. Structural studies provide the evidence that pMeO (one of the synthesized compounds) is an example of amides having no intermolecular hydrogen bonding in solid structure. In the BChE inhibition assay, compound (oMeO) having strong intermolecular force in the solid structure is less active than the compound (pMeO) with weak intermolecular forces in the solid structure. The docking studies proved that hydrogen bonding between inhibitor and BChE enzyme is of more importance for the activity, rather than intermolecular hydrogen bonding in the solid structure of inhibitor.

Optimized hydrophobic interactions and hydrogen bonding at the target-ligand interface leads the pathways of drug-designing.

PubMed

Patil, Rohan; Das, Suranjana; Stanley, Ashley; Yadav, Lumbani; Sudhakar, Akulapalli; Varma, Ashok K

2010-08-16

Weak intermolecular interactions such as hydrogen bonding and hydrophobic interactions are key players in stabilizing energetically-favored ligands, in an open conformational environment of protein structures. However, it is still poorly understood how the binding parameters associated with these interactions facilitate a drug-lead to recognize a specific target and improve drugs efficacy. To understand this, comprehensive analysis of hydrophobic interactions, hydrogen bonding and binding affinity have been analyzed at the interface of c-Src and c-Abl kinases and 4-amino substituted 1H-pyrazolo [3, 4-d] pyrimidine compounds. In-silico docking studies were performed, using Discovery Studio software modules LigandFit, CDOCKER and ZDOCK, to investigate the role of ligand binding affinity at the hydrophobic pocket of c-Src and c-Abl kinase. Hydrophobic and hydrogen bonding interactions of docked molecules were compared using LigPlot program. Furthermore, 3D-QSAR and MFA calculations were scrutinized to quantify the role of weak interactions in binding affinity and drug efficacy. The in-silico method has enabled us to reveal that a multi-targeted small molecule binds with low affinity to its respective targets. But its binding affinity can be altered by integrating the conformationally favored functional groups at the active site of the ligand-target interface. Docking studies of 4-amino-substituted molecules at the bioactive cascade of the c-Src and c-Abl have concluded that 3D structural folding at the protein-ligand groove is also a hallmark for molecular recognition of multi-targeted compounds and for predicting their biological activity. The results presented here demonstrate that hydrogen bonding and optimized hydrophobic interactions both stabilize the ligands at the target site, and help alter binding affinity and drug efficacy.

Optimized Hydrophobic Interactions and Hydrogen Bonding at the Target-Ligand Interface Leads the Pathways of Drug-Designing

PubMed Central

Stanley, Ashley; Yadav, Lumbani; Sudhakar, Akulapalli; Varma, Ashok K.

2010-01-01

Background Weak intermolecular interactions such as hydrogen bonding and hydrophobic interactions are key players in stabilizing energetically-favored ligands, in an open conformational environment of protein structures. However, it is still poorly understood how the binding parameters associated with these interactions facilitate a drug-lead to recognize a specific target and improve drugs efficacy. To understand this, comprehensive analysis of hydrophobic interactions, hydrogen bonding and binding affinity have been analyzed at the interface of c-Src and c-Abl kinases and 4-amino substituted 1H-pyrazolo [3, 4-d] pyrimidine compounds. Methodology In-silico docking studies were performed, using Discovery Studio software modules LigandFit, CDOCKER and ZDOCK, to investigate the role of ligand binding affinity at the hydrophobic pocket of c-Src and c-Abl kinase. Hydrophobic and hydrogen bonding interactions of docked molecules were compared using LigPlot program. Furthermore, 3D-QSAR and MFA calculations were scrutinized to quantify the role of weak interactions in binding affinity and drug efficacy. Conclusions The in-silico method has enabled us to reveal that a multi-targeted small molecule binds with low affinity to its respective targets. But its binding affinity can be altered by integrating the conformationally favored functional groups at the active site of the ligand-target interface. Docking studies of 4-amino-substituted molecules at the bioactive cascade of the c-Src and c-Abl have concluded that 3D structural folding at the protein-ligand groove is also a hallmark for molecular recognition of multi-targeted compounds and for predicting their biological activity. The results presented here demonstrate that hydrogen bonding and optimized hydrophobic interactions both stabilize the ligands at the target site, and help alter binding affinity and drug efficacy. PMID:20808434

Structure–kinetic relationship study of CDK8/CycC specific compounds

PubMed Central

Schneider, Elisabeth V.; Böttcher, Jark; Huber, Robert; Maskos, Klaus; Neumann, Lars

2013-01-01

In contrast with the very well explored concept of structure–activity relationship, similar studies are missing for the dependency between binding kinetics and compound structure of a protein ligand complex, the structure–kinetic relationship. Here, we present a structure–kinetic relationship study of the cyclin-dependent kinase 8 (CDK8)/cyclin C (CycC) complex. The scaffold moiety of the compounds is anchored in the kinase deep pocket and extended with diverse functional groups toward the hinge region and the front pocket. These variations can cause the compounds to change from fast to slow binding kinetics, resulting in an improved residence time. The flip of the DFG motif (“DMG” in CDK8) to the inactive DFG-out conformation appears to have relatively little influence on the velocity of binding. Hydrogen bonding with the kinase hinge region contributes to the residence time but has less impact than hydrophobic complementarities within the kinase front pocket. PMID:23630251

ERDA's Chemical Energy Storage Program

NASA Technical Reports Server (NTRS)

Swisher, J. H.; Kelley, J. H.

1977-01-01

The Chemical Energy Storage Program is described with emphasis on hydrogen storage. Storage techniques considered include pressurized hydrogen gas storage, cryogenic liquid hydrogen storage, storage in hydride compounds, and aromatic-alicyclic hydrogen storage. Some uses of energy storage are suggested. Information on hydrogen production and hydrogen use is also presented. Applications of hydrogen energy systems include storage of hydrogen for utilities load leveling, industrial marketing of hydrogen both as a chemical and as a fuel, natural gas supplementation, vehicular applications, and direct substitution for natural gas.

Hydrogen bonded supra-molecular framework in inorganic-organic hybrid compounds: Syntheses, structures, and photoluminescent properties

NASA Astrophysics Data System (ADS)

Yan, Li; Liu, Wei; Li, Chuanbi; Wang, Yifei; Ma, Li; Dong, Qinqin

2013-03-01

Two novel compounds constructed from aromatic acid and N-Heterocyclic ligands have been synthesized by hydrothermal reaction: [Cd(mip)(1,8-NDC)(H2O)]2 (1) [mip = 2-(3-methoxyphenyl)-1H-imidazo[4,5-f][1,10]phenanthroline, 1,8-NDC = naphthalene-1,8-dicarboxylic acid] and Cd(mip)2(NTC)2 (2) [NTC = nicotinic acid]. Compounds 1 and 2 are characterized by elemental analysis, IR, single crystal X-ray diffraction and thermogravimetric analysis (TGA). Single-crystal X-ray investigation reveals that compounds 1-2 are 0 dimensional (0D) structures, and the existence of hydrogen bonds and π-π interactions lead the 0D to 2D novel framework. Hydrogen bonds and π-π interactions are powerful non-covalent intermolecular interactions for directing supra-molecular architectures. TG analysis shows clear courses of weight loss, which corresponds to the decomposition of different ligands. At room temperature, compound 1 exhibits emission at 449 nm upon excitation at 325 nm, and compound 2 shows a strong emission at 656 nm upon excitation at 350 nm. Fluorescent spectrum displays that compounds 1 and 2 are potential luminescent materials.

Electrosorption of organic acids from aqueous bio-oil and conversion into hydrogen via microbial electrolysis cells

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

Park, Lydia Kyoung-Eun; Satinover, Scott J.; Yiacoumi, Sotira

Neutralization of the bio-oil pH has been shown to generate a neutralized bio-oil aqueous phase (NBOAP) that includes most of the acidic components and a neutralized bio-oil organic phase (NBOOP) that includes hydrophobic organics, such as phenols. NBOOP can be used for fuel production, while NBOAP can be fed to microbial electrolysis cells (MECs) for hydrogen production. After pH neutralization, some organic acidic components remain in NBOOP. This work is focused on capturing acidic compounds from NBOOP through water extraction and electrosorption, and demonstrating hydrogen production via MECs. Capacitive deionization (CDI) is proven effective in capturing ions from NBOOP-contacted watermore » and NBOAP via electrosorption. Captured acidic compounds enable the MEC application to effectively produce renewable hydrogen. Chemical oxygen demand (COD) removal of 49.2%, 61.5%, and 60.8% for 2, 4, and 10 g/L-anode/day loading were observed, corresponding to a total COD degradation of 0.19 g/L, 0.79 g/L, and 1.3 g/L, respectively. A maximum hydrogen productivity of 4.3 L-H 2/L-anode/day was obtained. Major compounds in the water phase such as fatty acids, sugar derivatives, furanic and phenolic compounds were converted to hydrogen with an efficiency of 80–90%. Lastly, this approach may lead the entire biomass pyrolysis process to be an overall carbon-neutral process.« less

Electrosorption of organic acids from aqueous bio-oil and conversion into hydrogen via microbial electrolysis cells

DOE PAGES

Park, Lydia Kyoung-Eun; Satinover, Scott J.; Yiacoumi, Sotira; ...

2018-02-17

Neutralization of the bio-oil pH has been shown to generate a neutralized bio-oil aqueous phase (NBOAP) that includes most of the acidic components and a neutralized bio-oil organic phase (NBOOP) that includes hydrophobic organics, such as phenols. NBOOP can be used for fuel production, while NBOAP can be fed to microbial electrolysis cells (MECs) for hydrogen production. After pH neutralization, some organic acidic components remain in NBOOP. This work is focused on capturing acidic compounds from NBOOP through water extraction and electrosorption, and demonstrating hydrogen production via MECs. Capacitive deionization (CDI) is proven effective in capturing ions from NBOOP-contacted watermore » and NBOAP via electrosorption. Captured acidic compounds enable the MEC application to effectively produce renewable hydrogen. Chemical oxygen demand (COD) removal of 49.2%, 61.5%, and 60.8% for 2, 4, and 10 g/L-anode/day loading were observed, corresponding to a total COD degradation of 0.19 g/L, 0.79 g/L, and 1.3 g/L, respectively. A maximum hydrogen productivity of 4.3 L-H 2/L-anode/day was obtained. Major compounds in the water phase such as fatty acids, sugar derivatives, furanic and phenolic compounds were converted to hydrogen with an efficiency of 80–90%. Lastly, this approach may lead the entire biomass pyrolysis process to be an overall carbon-neutral process.« less

Tritium labeling of antisense oligonucleotides by exchange with tritiated water.

PubMed Central

Graham, M J; Freier, S M; Crooke, R M; Ecker, D J; Maslova, R N; Lesnik, E A

1993-01-01

We describe a simple, efficient, procedure for labeling oligonucleotides to high specific activity (< 1 x 10(8) cpm/mumol) by hydrogen exchange with tritiated water at the C8 positions of purines in the presence of beta-mercaptoethanol, an effective radical scavenger. Approximately 90% of the starting material is recovered as intact, labeled oligonucleotide. The radiolabeled compounds are stable in biological systems; greater than 90% of the specific activity is retained after 72 hr incubation at 37 degrees C in serum-containing media. Data obtained from in vitro cellular uptake experiments using oligonucleotides labeled by this method are similar to those obtained using 35S or 14C-labeled compounds. Because this protocol is solely dependent upon the existence of purine residues, it should be useful for radiolabeling modified as well as unmodified phosphodiester oligonucleotides. Images PMID:8367289

The Strength of Hydrogen Bonds between Fluoro-Organics and Alcohols, a Theoretical Study.

PubMed

Rosenberg, Robert E

2018-05-10

Fluorinated organic compounds are ubiquitous in the pharmaceutical and agricultural industries. To better discern the mode of action of these compounds, it is critical to understand the strengths of hydrogen bonds involving fluorine. There are only a few published examples of the strengths of these bonds. This study provides a high level ab initio study of inter- and intramolecular hydrogen bonds between RF and R'OH, where R and R' are aryl, vinyl, alkyl, and cycloalkyl. Intermolecular binding energies average near 5 kcal/mol, while intramolecular binding energies average about 3 kcal/mol. Inclusion of zero-point energies and applying a counterpoise correction lessen the difference. In both series, modest increases in binding energies are seen with increased acidity of R'OH and increased electron donation of R in RF. In the intramolecular compounds, binding energy increases with the rigidity of the F-(C) n -OH ring. Inclusion of free energy corrections at 298 K results in exoergic binding energies for the intramolecular compounds and endoergic binding energies for the intermolecular compounds. Parameters such as bond lengths, vibrational frequencies, and atomic populations are consistent with formation of a hydrogen bond and with slightly stronger binding in the intermolecular cases over the intramolecular cases. However, these parameters correlated poorly with binding energies.

Process and composition for drying of gaseous hydrogen halides

DOEpatents

Tom, Glenn M.; Brown, Duncan W.

1989-08-01

A process for drying a gaseous hydrogen halide of the formula HX, wherein X is selected from the group consisting of bromine, chlorine, fluorine, and iodine, to remove water impurity therefrom, comprising: contacting the water impurity-containing gaseous hydrogen halide with a scavenger including a support having associated therewith one or more members of the group consisting of: (a) an active scavenging moiety selected from one or more members of the group consisting of: (i) metal halide compounds dispersed in the support, of the formula MX.sub.y ; and (ii) metal halide pendant functional groups of the formula -MX.sub.y-1 covalently bonded to the support, wherein M is a y-valent metal, and y is an integer whose value is from 1 to 3; (b) corresponding partially or fully alkylated compounds and/or pendant functional groups, of the metal halide compounds and/or pendant functional groups of (a); wherein the alkylated compounds and/or pendant functional groups, when present, are reactive with the gaseous hydrogen halide to form the corresponding halide compounds and/or pendant functional groups of (a); and M being selected such that the heat of formation, .DELTA.H.sub.f of its hydrated halide, MX.sub.y.(H.sub.2 O).sub.n, is governed by the relationship: .DELTA.H.sub.f .gtoreq.n.times.10.1 kilocalories/mole of such hydrated halide compound wherein n is the number of water molecules bound to the metal halide in the metal halide hydrate. Also disclosed is an appertaining scavenger composition and a contacting apparatus wherein the scavenger is deployed in a bed for contacting with the water impurity-containing gaseous hydrogen halide.

HYDROGENATION OF POLYCYCLIC AROMATIC COMPOUNDS USING NI SUPPORT ON H-BETA ZEOLITE IN SUPERCRITICAL CARBON DIOXIDE

EPA Science Inventory

The primary rationale for use of supercritical carbon dioxide as a solvent in hydrogenation is the elimination of mass transfer limitations, through enhancement of the solubility of hydrogen at the reaction locus. Hydrogenation of anthracene was performed using NiHB-zeolite catal...

Purification of Hydrogen

DOEpatents

Newton, A S

1950-12-05

Disclosed is a process for purifying hydrogen containing various gaseous impurities by passing the hydrogen over a large surface of uranium metal at a temperature above the decomposition temperature of uranium hydride, and below the decomposition temperature of the compounds formed by the combination of the uranium with the impurities in the hydrogen.

Single-catalyst high-weight% hydrogen storage in an N-heterocycle synthesized from lignin hydrogenolysis products and ammonia

PubMed Central

Forberg, Daniel; Schwob, Tobias; Zaheer, Muhammad; Friedrich, Martin; Miyajima, Nobuyoshi; Kempe, Rhett

2016-01-01

Large-scale energy storage and the utilization of biomass as a sustainable carbon source are global challenges of this century. The reversible storage of hydrogen covalently bound in chemical compounds is a particularly promising energy storage technology. For this, compounds that can be sustainably synthesized and that permit high-weight% hydrogen storage would be highly desirable. Herein, we report that catalytically modified lignin, an indigestible, abundantly available and hitherto barely used biomass, can be harnessed to reversibly store hydrogen. A novel reusable bimetallic catalyst has been developed, which is able to hydrogenate and dehydrogenate N-heterocycles most efficiently. Furthermore, a particular N-heterocycle has been identified that can be synthesized catalytically in one step from the main lignin hydrogenolysis product and ammonia, and in which the new bimetallic catalyst allows multiple cycles of high-weight% hydrogen storage. PMID:27762267

Single-catalyst high-weight% hydrogen storage in an N-heterocycle synthesized from lignin hydrogenolysis products and ammonia.

PubMed

Forberg, Daniel; Schwob, Tobias; Zaheer, Muhammad; Friedrich, Martin; Miyajima, Nobuyoshi; Kempe, Rhett

2016-10-20

Large-scale energy storage and the utilization of biomass as a sustainable carbon source are global challenges of this century. The reversible storage of hydrogen covalently bound in chemical compounds is a particularly promising energy storage technology. For this, compounds that can be sustainably synthesized and that permit high-weight% hydrogen storage would be highly desirable. Herein, we report that catalytically modified lignin, an indigestible, abundantly available and hitherto barely used biomass, can be harnessed to reversibly store hydrogen. A novel reusable bimetallic catalyst has been developed, which is able to hydrogenate and dehydrogenate N-heterocycles most efficiently. Furthermore, a particular N-heterocycle has been identified that can be synthesized catalytically in one step from the main lignin hydrogenolysis product and ammonia, and in which the new bimetallic catalyst allows multiple cycles of high-weight% hydrogen storage.

Scales of Hydrogen-Bonding Workshop Held in London, England on 1-3 July 1987

DTIC Science & Technology

1987-07-03

medium (a perfluorinated compound , FC-75), hoping to attain the basicity of CF3 CH2OH and (CF 3.2CHOH. The frequency shifts of the 3818 cm v(OH) band of...bond basicity for nonassoclated compounds , pro.ided that the reference acids in each case led toi*values that were almost the same - around 65". ’ 1...experimental measurements JOSE-LOUIS M. ABBOUD * The hydrogen-bonding basicity of oxygen and sulphur compounds MICHAEL H. ABRAHAM, PRISCILLA L

Urea and deuterium mixtures at high pressures

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

Donnelly, M., E-mail: m.donnelly-2@sms.ed.ac.uk; Husband, R. J.; Frantzana, A. D.

2015-03-28

Urea, like many network forming compounds, has long been known to form inclusion (guest-host) compounds. Unlike other network formers like water, urea is not known to form such inclusion compounds with simple molecules like hydrogen. Such compounds if they existed would be of interest both for the fundamental insight they provide into molecular bonding and as potential gas storage systems. Urea has been proposed as a potential hydrogen storage material [T. A. Strobel et al., Chem. Phys. Lett. 478, 97 (2009)]. Here, we report the results of high-pressure neutron diffraction studies of urea and D{sub 2} mixtures that indicate nomore » inclusion compound forms up to 3.7 GPa.« less

Carbon Dioxide Hydrogenation into Higher Hydrocarbons and Oxygenates: Thermodynamic and Kinetic Bounds and Progress with Heterogeneous and Homogeneous Catalysis.

PubMed

Prieto, Gonzalo

2017-03-22

Under specific scenarios, the catalytic hydrogenation of CO 2 with renewable hydrogen is considered a suitable route for the chemical recycling of this environmentally harmful and chemically refractory molecule into added-value energy carriers and chemicals. The hydrogenation of CO 2 into C 1 products, such as methane and methanol, can be achieved with high selectivities towards the corresponding hydrogenation product. More challenging, however, is the selective production of high (C 2+ ) hydrocarbons and oxygenates. These products are desired as energy vectors, owing to their higher volumetric energy density and compatibility with the current fuel infrastructure than C 1 compounds, and as entry platform chemicals for existing value chains. The major challenge is the optimal integration of catalytic functionalities for both reductive and chain-growth steps. This Minireview summarizes the progress achieved towards the hydrogenation of CO 2 to C 2+ hydrocarbons and oxygenates, covering both solid and molecular catalysts and processes in the gas and liquid phases. Mechanistic aspects are discussed with emphasis on intrinsic kinetic limitations, in some cases inevitably linked to thermodynamic bounds through the concomitant reverse water-gas-shift reaction, which should be considered in the development of advanced catalysts and processes. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Boronate probes as diagnostic tools for real time monitoring of peroxynitrite and hydroperoxides

PubMed Central

Zielonka, Jacek; Sikora, Adam; Hardy, Micael; Joseph, Joy; Dranka, Brian P.; Kalyanaraman, Balaraman

2012-01-01

Boronates, a group of organic compounds, are emerging as one of the most effective probes for detecting and quantifying peroxynitrite, hypochlorous acid and hydrogen peroxide. Boronates react with peroxynitrite nearly a million times faster than with hydrogen peroxide. Boronate-containing fluorogenic compounds have been used to monitor real time generation of peroxynitrite in cells and for imaging hydrogen peroxide in living animals. This Perspective highlights potential applications of boronates and other fluorescent probes to high-throughput analyses of peroxynitrite and hydroperoxides in toxicological studies. PMID:22731669

Use of Compound-Specific Stable Isotope Analysis to Distinguish Between Vapor Intrusion and Indoor Sources of VOCs - CSIA Protocol for Vapor Intrusion Investigations

DTIC Science & Technology

2014-07-01

Analyzer TCE Trichloroethene USEPA U.S. Environmental Protection Agency V- PDB Vienna - Pee Dee Belemnite V-SMOW Vienna – Standard Mean Ocean Water ... PDB ) for carbon, Standard Mean Ocean Chloride (SMOC) for chlorine, and Vienna-Standard Mean Ocean Water (V-SMOW) for hydrogen. CSIA Protocol for...7 3.3 INDOOR AIR SAMPLING LOCATIONS ............................................................ 8 3.4 COLLECTION OF WATER SAMPLES

Tandem sulfur chemiluminescence and flame ionization detection with planar microfluidic devices for the characterization of sulfur compounds in hydrocarbon matrices.

PubMed

Luong, J; Gras, R; Shellie, R A; Cortes, H J

2013-07-05

The detection of sulfur compounds in different hydrocarbon matrices, from light hydrocarbon feedstocks to medium synthetic crude oil feeds provides meaningful information for optimization of refining processes as well as demonstration of compliance with petroleum product specifications. With the incorporation of planar microfluidic devices in a novel chromatographic configuration, sulfur compounds from hydrogen sulfide to alkyl dibenzothiophenes and heavier distributions of sulfur compounds over a wide range of matrices spanning across a boiling point range of more than 650°C can be characterized, using one single analytical configuration in less than 25min. In tandem with a sulfur chemiluminescence detector for sulfur analysis is a flame ionization detector. The flame ionization detector can be used to establish the boiling point range of the sulfur compounds in various hydrocarbon fractions for elemental specific simulated distillation analysis as well as profiling the hydrocarbon matrices for process optimization. Repeatability of less than 3% RSD (n=20) over a range of 0.5-1000 parts per million (v/v) was obtained with a limit of detection of 50 parts per billion and a linear range of 0.5-1000 parts per million with a correlation co-efficient of 0.998. Copyright © 2013 Elsevier B.V. All rights reserved.

The Potential of Isotope Ratio Mass Spectrometry (IRMS) and Gas Chromatography-IRMS Analysis of Triacetone Triperoxide in Forensic Explosives Investigations.

PubMed

Bezemer, Karlijn D B; Koeberg, Mattijs; van der Heijden, Antoine E D M; van Driel, Chris A; Blaga, Cornelia; Bruinsma, Jildert; van Asten, Arian C

2016-09-01

Studying links between triacetone triperoxide (TATP) samples from crime scenes and suspects can assist in criminal investigations. Isotope ratio mass spectrometry (IRMS) and gas chromatography (GC)-IRMS were used to measure the isotopic compositions of TATP and its precursors acetone and hydrogen peroxide. In total, 31 TATP samples were synthesized with different raw material combinations and reaction conditions. For carbon, a good differentiation and a linear relationship were observed for acetone-TATP combinations. The extent of negative (δ(13) C) fractionation depended on the reaction yield. Limited enrichment was observed for the hydrogen isotope (δ(2) H) values of the TATP samples probably due to a constant exchange of hydrogen atoms in aqueous solution. For oxygen (δ(18) O), the small isotopic range and excess of water in hydrogen peroxide resulted in poor differentiation. GC-IRMS and IRMS data were comparable except for one TATP sample prepared with high acid concentration demonstrating the potential of compound-specific isotope analysis. Carbon IRMS has practical use in forensic TATP investigations. © 2016 American Academy of Forensic Sciences.

Is modern climate variability reflected in compund specific hydrogen isotope ratios of sedimentary biomarkers?

NASA Astrophysics Data System (ADS)

Sachse, D.; Radke, J.; Gleixner, G.

2003-04-01

Compound specific hydrogen isotope ratios are emerging as a new palaeoclimatic and palaeohydrological proxy. First reconstructions of palaeoclimate using D/H ratios from n-alkanes are available (Andersen et al. 2001, Sauer et al. 2001, Sachse et al. 2003). However, a systematic approach comparing recent sedimentary biomarkers with climate data is still lacking. We are establishing an ecosystem study of small, ground water fed lakes with known limnology. Nearly all lakes are close to a long-term climate-monitoring site (CARBOEUROPE flux tower site, IAEA precipitation monitoring) delivering ecophysiological and climatic data as temperature, precipitation, evapotranspiration etc. Water, primary biomass, plant, soil and sediment were sampled from lakes and the surrounding ecosystem along a climatic and isotopic gradient in meteoric waters from northern Finland (deltaD: -130 permil vs. VSMOW) to southern Italy (deltaD: -30 permil vs. VSMOW, IAEA 2001). Biomarkers were extracted from the samples to test if climatic variability is reflected in their D/H ratios. First results of the factors influencing the hydrogen isotope composition of sedimentary biomarkers and their use as palaeoclimatic and palaeohydrological proxy will be presented. Andersen N, Paul HA, Bernasconi SM, McKenzie JA, Behrens A, Schaeffer P, Albrecht P (2001) Large and rapid climate variability during the Messinian salinity crisis: Evidence from deuterium concentrations of individual biomarkers. Geology 29:799-802 IAEA (2001) GNIP Maps and Animations. International Atomic Energy Agency, Vienna. Accessible at http://isohis.iaea.org Sachse D, Radke J, Gaupp R, Schwark L, Lüniger G, Gleixner G (2003) Reconstruction of palaeohydrological conditions in a lagoon during the 2nd Zechstein cycle through simultaneous use of deltaD values of individual n-alkanes and delta18O and delta13C values of carbonates. International Journal of Earth Sciences, submitted Sauer PE, Eglington TI, Hayes JM, Schimmelman A, Sessions AL (2001) Compound-specific D/H ratios of lipid biomarkers from sediments as a proxy for environmental and climatic conditions. Geochimica et Cosmochimica Acta 65:213-222

Electrochemical Hydrogen Evolution at Ordered Mo 7 Ni 7

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

Csernica, Peter M.; McKone, James R.; Mulzer, Catherine R.

2017-04-11

Ni–Mo alloys containing up to ~15 mol % Mo are excellent non-noble electrocatalysts for the hydrogen evolution reaction (HER) in alkaline aqueous electrolytes. To date, studies have not addressed the details of HER activity of ordered Ni–Mo intermetallic compounds, which can contain a significantly larger fraction of Mo (up to 50 mol %) than can be accessed through high-temperature alloying. Here, we present a straightforward and facile synthesis of three phase-pure electrocatalyst powders using a precipitation–reduction approach: ordered Mo7Ni7, disordered Ni0.92Mo0.08, and pure Ni. The Ni0.92Mo0.08 alloy exhibited a nearly 10-fold higher mass-specific HER activity than either pure Ni ormore » Mo7Ni7, where much of the difference could be attributed to relative surface area. Therefore, we attempted to quantify and account for differences in surface areas using electron microscopy, impedance spectroscopy, and gas adsorption measurements. These data suggest that Ni–Mo alloys and intermetallic compounds exhibit substantial pseudocapacitance at potentials near the onset of hydrogen evolution, which can cause impedance spectroscopy to overestimate the interfacial capacitance, and thus the electrochemically active surface area, of these materials. From these observations, we postulate Mo redox activity as the chemical basis for the observed pseudocapacitance of Ni–Mo composites. Furthermore, using gas adsorption measurements, rather than capacitance, to estimate active surface area, we find that ordered Mo7Ni7 is more intrinsically active than the Ni0.92Mo0.08 alloy, implying that Mo7Ni7 intermetallics with high surface area will also give higher mass-specific activities than alloys with comparable roughness.« less

Intermetallic nickel silicide nanocatalyst—A non-noble metal–based general hydrogenation catalyst

PubMed Central

Pohl, Marga-Martina; Agapova, Anastasiya

2018-01-01

Hydrogenation reactions are essential processes in the chemical industry, giving access to a variety of valuable compounds including fine chemicals, agrochemicals, and pharmachemicals. On an industrial scale, hydrogenations are typically performed with precious metal catalysts or with base metal catalysts, such as Raney nickel, which requires special handling due to its pyrophoric nature. We report a stable and highly active intermetallic nickel silicide catalyst that can be used for hydrogenations of a wide range of unsaturated compounds. The catalyst is prepared via a straightforward procedure using SiO2 as the silicon atom source. The process involves thermal reduction of Si–O bonds in the presence of Ni nanoparticles at temperatures below 1000°C. The presence of silicon as a secondary component in the nickel metal lattice plays the key role in its properties and is of crucial importance for improved catalytic activity. This novel catalyst allows for efficient reduction of nitroarenes, carbonyls, nitriles, N-containing heterocycles, and unsaturated carbon–carbon bonds. Moreover, the reported catalyst can be used for oxidation reactions in the presence of molecular oxygen and is capable of promoting acceptorless dehydrogenation of unsaturated N-containing heterocycles, opening avenues for H2 storage in organic compounds. The generality of the nickel silicide catalyst is demonstrated in the hydrogenation of over a hundred of structurally diverse unsaturated compounds. The wide application scope and high catalytic activity of this novel catalyst make it a nice alternative to known general hydrogenation catalysts, such as Raney nickel and noble metal–based catalysts. PMID:29888329

Formation of the low-resistivity compound Cu{sub 3}Ge by low-temperature treatment in an atomic hydrogen flux

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

Erofeev, E. V., E-mail: erofeev@micran.ru; Kazimirov, A. I.; Fedin, I. V.

The systematic features of the formation of the low-resistivity compound Cu{sub 3}Ge by low-temperature treatment of a Cu/Ge two-layer system in an atomic hydrogen flux are studied. The Cu/Ge two-layer system is deposited onto an i-GaAs substrate. Treatment of the Cu/Ge/i-GaAs system, in which the layer thicknesses are, correspondingly, 122 and 78 nm, in atomic hydrogen with a flux density of 10{sup 15} at cm{sup 2} s{sup –1} for 2.5–10 min at room temperature induces the interdiffusion of Cu and Ge, with the formation of a polycrystalline film containing the stoichiometric Cu{sub 3}Ge phase. The film consists of vertically orientedmore » grains 100–150 nm in size and exhibits a minimum resistivity of 4.5 µΩ cm. Variations in the time of treatment of the Cu/Ge/i-GaAs samples in atomic hydrogen affect the Cu and Ge depth distribution, the phase composition of the films, and their resistivity. Experimental observation of the synthesis of the Cu{sub 3}Ge compound at room temperature suggests that treatment in atomic hydrogen has a stimulating effect on both the diffusion of Cu and Ge and the chemical reaction of Cu{sub 3}Ge-compound formation. These processes can be activated by the energy released upon the recombination of hydrogen atoms adsorbed at the surface of the Cu/Ge/i-GaAs sample.« less

Intermetallic nickel silicide nanocatalyst-A non-noble metal-based general hydrogenation catalyst.

PubMed

Ryabchuk, Pavel; Agostini, Giovanni; Pohl, Marga-Martina; Lund, Henrik; Agapova, Anastasiya; Junge, Henrik; Junge, Kathrin; Beller, Matthias

2018-06-01

Hydrogenation reactions are essential processes in the chemical industry, giving access to a variety of valuable compounds including fine chemicals, agrochemicals, and pharmachemicals. On an industrial scale, hydrogenations are typically performed with precious metal catalysts or with base metal catalysts, such as Raney nickel, which requires special handling due to its pyrophoric nature. We report a stable and highly active intermetallic nickel silicide catalyst that can be used for hydrogenations of a wide range of unsaturated compounds. The catalyst is prepared via a straightforward procedure using SiO 2 as the silicon atom source. The process involves thermal reduction of Si-O bonds in the presence of Ni nanoparticles at temperatures below 1000°C. The presence of silicon as a secondary component in the nickel metal lattice plays the key role in its properties and is of crucial importance for improved catalytic activity. This novel catalyst allows for efficient reduction of nitroarenes, carbonyls, nitriles, N-containing heterocycles, and unsaturated carbon-carbon bonds. Moreover, the reported catalyst can be used for oxidation reactions in the presence of molecular oxygen and is capable of promoting acceptorless dehydrogenation of unsaturated N-containing heterocycles, opening avenues for H 2 storage in organic compounds. The generality of the nickel silicide catalyst is demonstrated in the hydrogenation of over a hundred of structurally diverse unsaturated compounds. The wide application scope and high catalytic activity of this novel catalyst make it a nice alternative to known general hydrogenation catalysts, such as Raney nickel and noble metal-based catalysts.

Raman Spectroscopy of Cocrystals

NASA Astrophysics Data System (ADS)

Rooney, Frank; Reardon, Paul; Ochoa, Romulo; Abourahma, Heba; Marti, Marcus; Dimeo, Rachel

2010-02-01

Cocrystals are a class of compounds that consist of two or more molecules that are held together by hydrogen bonding. Pharmaceutical cocrystals are those that contain an active pharmaceutical ingredient (API) as one of the components. Pharmaceutical cocrystals are of particular interest and have gained a lot of attention in recent years because they offer the ability to modify the physical properties of the API, like solubility and bioavailability, without altering the chemical structure of the API. The APIs that we targeted for our studies are theophylline (Tp) and indomethacin (Ind). These compounds have been mixed with complementary coformers (cocrystal former) that include acetamide (AcONH2), melamine (MLM), nicotinic acid (Nic-COOH), 4-cyanopyridine (4-CNPy) and 4-aminopyridine (4-NH2Py). Raman spectroscopy has been used to characterize these cocrystals. Spectra of the cocrystals were compared to those of the coformers to analyze for peak shifts, specifically those corresponding to hydrogen bonding. A 0.5 m CCD Spex spectrometer was used, in a micro-Raman setup, for spectral analysis. An Argon ion Coherent laser at 514.5 nm was used as the excitation source. )

CuNi Nanoparticles Assembled on Graphene for Catalytic Methanolysis of Ammonia Borane and Hydrogenation of Nitro/Nitrile Compounds

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

Yu, Chao; Fu, Jiaju; Muzzio, Michelle

Here we report a solution phase synthesis of 16 nm CuNi nanoparticles (NPs) with the Cu/Ni composition control. These NPs are assembled on graphene (G) and show Cu/Ni composition-dependent catalysis for methanolysis of ammonia borane (AB) and hydrogenation of aromatic nitro (nitrile) compounds to primary amines in methanol at room temperature. Among five different CuNi NPs studied, the G-Cu 36Ni 64 NPs are the best catalyst for both AB methanolysis (TOF = 49.1 mol H2 mol CuNi -1 min -1 and E a = 24.4 kJ/mol) and hydrogenation reactions (conversion yield >97%). In conclusion, the G-CuNi represents a unique noble-metal-freemore » catalyst for hydrogenation reactions in a green environment without using pure hydrogen.« less

High Density Hydrogen Storage System Demonstration Using NaAlH4 Based Complex Compound Hydrides

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

Daniel A. Mosher; Xia Tang; Ronald J. Brown

2007-07-27

This final report describes the motivations, activities and results of the hydrogen storage independent project "High Density Hydrogen Storage System Demonstration Using NaAlH4 Based Complex Compound Hydrides" performed by the United Technologies Research Center under the Department of Energy Hydrogen Program, contract # DE-FC36-02AL67610. The objectives of the project were to identify and address the key systems technologies associated with applying complex hydride materials, particularly ones which differ from those for conventional metal hydride based storage. This involved the design, fabrication and testing of two prototype systems based on the hydrogen storage material NaAlH4. Safety testing, catalysis studies, heat exchangermore » optimization, reaction kinetics modeling, thermochemical finite element analysis, powder densification development and material neutralization were elements included in the effort.« less

CuNi Nanoparticles Assembled on Graphene for Catalytic Methanolysis of Ammonia Borane and Hydrogenation of Nitro/Nitrile Compounds

DOE PAGES

Yu, Chao; Fu, Jiaju; Muzzio, Michelle; ...

2017-01-12

Here we report a solution phase synthesis of 16 nm CuNi nanoparticles (NPs) with the Cu/Ni composition control. These NPs are assembled on graphene (G) and show Cu/Ni composition-dependent catalysis for methanolysis of ammonia borane (AB) and hydrogenation of aromatic nitro (nitrile) compounds to primary amines in methanol at room temperature. Among five different CuNi NPs studied, the G-Cu 36Ni 64 NPs are the best catalyst for both AB methanolysis (TOF = 49.1 mol H2 mol CuNi -1 min -1 and E a = 24.4 kJ/mol) and hydrogenation reactions (conversion yield >97%). In conclusion, the G-CuNi represents a unique noble-metal-freemore » catalyst for hydrogenation reactions in a green environment without using pure hydrogen.« less

The synthesis and structures of 1,1'-bis(sulfonyl)ferrocene derivatives.

PubMed

Chanawanno, Kullapa; Holstrom, Cole; Crandall, Laura A; Dodge, Henry; Nemykin, Victor N; Herrick, Richard S; Ziegler, Christopher J

2016-09-28

A series of 1,1'-bis(sulfonyl)ferrocene compounds were produced via the 1,1'-bis(sulfonate)ferrocene ammonium salt. This compound can be readily converted to 1,1' bis(sulfonylchloride)ferrocene. By varying stoichiometry and reaction times, both mono- and bis-sulfonamide derivatives can be synthesized. All new compounds presented in this report have been structurally characterized. The structures of the bis-sulfonamide systems are similar to the well-studied bis(amide) ferrocene compounds. Intermolecular hydrogen bonding is observed, typically between NH and SO groups of neighboring sulfonamides. However in the bis(GABA) derivative, intermolecular NH to CO hydrogen bonding interactions are present.

Structural characterization of human heme oxygenase-1 in complex with azole-based inhibitors.

PubMed

Rahman, Mona N; Vlahakis, Jason Z; Roman, Gheorghe; Vukomanovic, Dragic; Szarek, Walter A; Nakatsu, Kanji; Jia, Zongchao

2010-03-01

The development of inhibitors specific for heme oxygenases (HO) aims to provide powerful tools in understanding the HO system. Based on the lead structure (2S, 4S)-2-[2-(4-chlorophenyl)ethyl]-2-[(1H-imidazol-1-yl)methyl]-4-[((4-aminophenyl)thio)methyl]-1,3-dioxolane (azalanstat, QC-1) we have synthesized structural modifications to develop novel and selective HO inhibitors. The structural study of human HO-1 (hHO-1) in complex with a select group of the inhibitors was initiated using X-ray crystallographic techniques. Comparison of the structures of four such compounds each in complex with hHO-1 revealed a common binding mode, despite having different structural fragments. The compounds bind to the distal side of heme through an azole "anchor" which coordinates with the heme iron. An expansion of the distal pocket, mainly due to distal helix flexibility, allows accommodation of the compounds without displacing heme or the critical Asp140 residue. Rather, binding displaces a catalytically critical water molecule and disrupts an ordered hydrogen-bond network involving Asp140. The presence of a triazole "anchor" may provide further stability via a hydrogen bond with the protein. A hydrophobic pocket acts to stabilize the region occupied by the phenyl or adamantanyl moieties of these compounds. Further, a secondary hydrophobic pocket is formed via "induced fit" to accommodate bulky substituents at the 4-position of the dioxolane ring. Copyright 2009 Elsevier Inc. All rights reserved.

Crystallographic studies on complexes of potassium iodide and copper perchlorate with N, Nʹ-dicyclohexylurea tethered to a benzo-12-crown-4

NASA Astrophysics Data System (ADS)

Tripathi, Garima; Ramanathan, Gurunath

2018-03-01

The N, N‧-dicyclohexylurea-capped benzo-12-crown-4 (compound 1) has been synthesized. The coordination behaviour of this compound (1) has been studied by crystallizing it with KI (2) and Cu(ClO4)2 (3) salts. The crystallographic studies were performed with all three compounds. The presence of metal ions significantly affects the crystal packing of the compound 1. The crystal lattice of compound 1 was stabilized by Csbnd H⋯π and Cdbnd O⋯Hsbnd N hydrogen bonding. The presence of KI in compound 2 results in a dimer structure in which iodide anion behaves as a bridging ligand. The K+ forms a perching structure with the crown ring. In the compound 3, Cu2+ ion and ligand molecule (1) crystallized independently. They were connected through hydrogen bonding. Interestingly, Cu2+ adopts two different geometries with the coordination number 5 and 6. The centre Cu2+ (Cu1) adopted an octahedral geometry whereas the terminal Cu2+ (Cu2) acquired square pyramidal geometry. The coordination sphere of Cu2+ contains ClO4- anion and water molecules. Cu2+ ion forms a chain structure through ClO4- anion and water molecules involve in hydrogen bonding with the ligand molecule.

Desulfurization of benzonaphthothiophenes and dibenzothiophene with a Raney nickel catalyst and its relationship to the. pi. -electron density

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

Nagai, M.; Urimoto, H.; Uetake, K.

The hydrodesulfurization of heavy petroleum feedstocks and coal-derived liquids requires the conversion of high molecular weight compounds like dibenzothiophene and benzonaphthothiophenes. There are several studies in the literature which deal with the mechanism of the hydrodesulfurization of multi-ring thiophenic compounds on cobalt or nickel molybdenum catalysts at high pressure. However, there are only a few studies which relate the chemical reactivity of these compounds to their electronic structure. The reactivity of a multi-ring sulfur-containing compound is not determined solely by the size of the molecule. In addition, others studied the relationship between the first step in the hydrotreating reaction ofmore » benzonaphthothiophene and the Coulombic interaction term of the compounds using the CNDO/S method. Because there is competition between the different processes (hydrogenation and desulfurization) during reaction, it is difficult to understand the relationship between desulfurization and the electronic properties of the compounds under reaction conditions. The calculation of electronic structures necessarily involves many sigma bonds of hydrogenated aromatic rings as well as many electrons of high molecular weight compounds. For this reason, it is best to select a catalyst and reaction conditions under which desulfurization takes place without hydrogenation.« less

Anti-ulcer agents: chemical aspect of solving the problem

NASA Astrophysics Data System (ADS)

Rogoza, L. N.; Salakhutdinov, N. F.

2015-01-01

The data on chemical structures and specific activities of compounds functioning as histamine H2-receptor antagonists, H+/K+-ATPase inhibitors at the exchange sites of hydrogen ions (proton pump inhibitors) and potassium ions (K+-competitive acid blockers) published from 1990 to 2013 are surveyed. The antisecretory agents with studied cytoprotective activity or with additional therapeutic properties compensating for disorders of internal defence mechanisms are presented. A separate section is devoted to the drugs that prevent or mitigate the NSAID-induced intestinal damage. All of the considered structures are classified according to the type of biological mechanism of action. Some aspects of the structure-activity relationships for such compounds are considered. The bibliography includes 83 references.

Monitoring BTEX degradation by CSIA - chances and challenges

NASA Astrophysics Data System (ADS)

Vogt, Carsten; Dorer, Conrad; Kümmel, Steffen; Bombach, Petra; Fischer, Anko; Richnow, Hans Hermann

2014-05-01

Monitoring is crucial for evaluating the success of any geobiotechnological applications. Compound- specific stable isotope analysis (CSIA) has emerged as a key method for monitoring biogeochemical transformation processes. Isotope compositions of residual reactants may change during the first rate-limiting step in (bio)chemical reactions; measurement of these changes are the basis for CSIA. Caused by differences in the activation energy, light isotopologues often react slightly faster than heavy isotopologues, resulting in enrichment of heavy isotopes at the reactive site in the substrate or of light isotopes in the product. This is termed isotope fractionation. Upon multi-dimensional CSIA (2D-CSIA, 3D-CSIA), the isotope fractionation of two or more different elements within a molecule is determined, allowing highly resolved analyses of degradation processes as masking effects typically occurring in one-dimensional CSIA are cancelled. In the last years, 2D-CSIA making use of the ratio of stable carbon to hydrogen isotopes (13C/12C, 2H/1H), turned out to be an important tool for elucidating the environmental biodegradation pattern of BTEX compounds which are global notorious contaminants. This presentation aims to summarize the current knowledge on 2D-CSIA of BTEX, to point out the prospects and to indicate future perspectives upon monitoring in the field. Degradation experiments for determining carbon and hydrogen isotope fractionation factors were carried out using several pure and mixed cultures performing different BTEX-activating reactions. Various anaerobic key reactions showed pronounced hydrogen isotope fractionation: (i) fumarate addition to the methyl moiety of toluene, xylene isomers and probably ethylbenzene catalyzed by benzylsuccinate synthases, (ii) anaerobic hydroxylation of the ethyl side chain of ethylbenzene catalyzed by ethylbenzene dehydrogenase, and (iii) anaerobic activation of benzene by yet unknown biochemical mechanisms. Due to the high hydrogen isotope fractionation, the ratios of hydrogen vs. carbon isotope fractionation in two-dimensional plots (lambda values, Λ) were generally higher than 10 (in extreme cases > 100). Upon aerobic activation reactions at the aromatic ring catalyzed by mono- or dioxygenases, usually Λ values smaller than 10 were observed due to small, absent or inverse hydrogen isotope fractionation. An exception is the aerobic monooxygenation of methyl or methylene moieties which is linked to large hydrogen and carbon isotope fractionation. Since Λ values are highly indicative for specific transformation reactions, 2D-CSIA has a great potential for evaluating biodegradation processes of BTEX in the environment. Moreover, reactions catalyzed by benzylsuccinate synthases showed partially variable Λ values, indicating slightly different reaction mechanisms of isoenzymes, probably permitting the detection of specific isoenzymes by 2D-CSIA in field applications. In contrast, ethylbenzene dehydrogenase of three tested organisms showed similar, very characteristic isotope fractionation pattern even under different redox conditions. The major goal of future investigations is to use 2D-CSIA at contaminated field sites for elucidating specific degradation pathways. Single data for benzene are promising, demonstrating e.g., anaerobic benzene degradation by 2D-CSIA at a highly contaminated site. Nevertheless, 2D-CSIA field data for BTEX are yet lacking and need to be surveyed for a proper evaluation of the 2D-CSIA concept for BTEX.

Carbonate thermochemical cycle for the production of hydrogen

DOEpatents

Collins, Jack L [Knoxville, TN; Dole, Leslie R [Knoxville, TN; Ferrada, Juan J [Knoxville, TN; Forsberg, Charles W [Oak Ridge, TN; Haire, Marvin J [Oak Ridge, TN; Hunt, Rodney D [Oak Ridge, TN; Lewis, Jr, Benjamin E [Knoxville, TN; Wymer, Raymond G [Oak Ridge, TN

2010-02-23

The present invention is directed to a thermochemical method for the production of hydrogen from water. The method includes reacting a multi-valent metal oxide, water and a carbonate to produce an alkali metal-multi-valent metal oxide compound, carbon dioxide, and hydrogen.

Catalytic Hydrogenation of Carbon Dioxide with Ammonia-Borane by Pincer-type Phosphorus Compound: A Theoretical Prediction.

PubMed

Zeng, Guixiang; Maeda, Satoshi; Taketsugu, Tetsuya; Sakaki, Shigeyoshi

2016-10-01

Theoretically designed pincer-type phosphorus compound is found to be active for the hydrogenation of carbon dioxide (CO 2 ) with ammonia-borane. DFT, ONIOM(CCSD(T):MP2), and CCSD(T) computational results demonstrated that the reaction occurs through the phosphorus-ligand cooperative catalysis function, which provides an unprecedented protocol for metal-free CO 2 conversion. The phosphorus compounds with the NNN ligand are more active than those with the ONO ligand. The conjugate and planar ligand considerably improves the efficiency of the catalyst.

Physicochemical characteristics of structurally determined metabolite-protein and drug-protein binding events with respect to binding specificity.

PubMed

Korkuć, Paula; Walther, Dirk

2015-01-01

To better understand and ultimately predict both the metabolic activities as well as the signaling functions of metabolites, a detailed understanding of the physical interactions of metabolites with proteins is highly desirable. Focusing in particular on protein binding specificity vs. promiscuity, we performed a comprehensive analysis of the physicochemical properties of compound-protein binding events as reported in the Protein Data Bank (PDB). We compared the molecular and structural characteristics obtained for metabolites to those of the well-studied interactions of drug compounds with proteins. Promiscuously binding metabolites and drugs are characterized by low molecular weight and high structural flexibility. Unlike reported for drug compounds, low rather than high hydrophobicity appears associated, albeit weakly, with promiscuous binding for the metabolite set investigated in this study. Across several physicochemical properties, drug compounds exhibit characteristic binding propensities that are distinguishable from those associated with metabolites. Prediction of target diversity and compound promiscuity using physicochemical properties was possible at modest accuracy levels only, but was consistently better for drugs than for metabolites. Compound properties capturing structural flexibility and hydrogen-bond formation descriptors proved most informative in PLS-based prediction models. With regard to diversity of enzymatic activities of the respective metabolite target enzymes, the metabolites benzylsuccinate, hypoxanthine, trimethylamine N-oxide, oleoylglycerol, and resorcinol showed very narrow process involvement, while glycine, imidazole, tryptophan, succinate, and glutathione were identified to possess broad enzymatic reaction scopes. Promiscuous metabolites were found to mainly serve as general energy currency compounds, but were identified to also be involved in signaling processes and to appear in diverse organismal systems (digestive and nervous system) suggesting specific molecular and physiological roles of promiscuous metabolites.

Physicochemical characteristics of structurally determined metabolite-protein and drug-protein binding events with respect to binding specificity

PubMed Central

Korkuć, Paula; Walther, Dirk

2015-01-01

To better understand and ultimately predict both the metabolic activities as well as the signaling functions of metabolites, a detailed understanding of the physical interactions of metabolites with proteins is highly desirable. Focusing in particular on protein binding specificity vs. promiscuity, we performed a comprehensive analysis of the physicochemical properties of compound-protein binding events as reported in the Protein Data Bank (PDB). We compared the molecular and structural characteristics obtained for metabolites to those of the well-studied interactions of drug compounds with proteins. Promiscuously binding metabolites and drugs are characterized by low molecular weight and high structural flexibility. Unlike reported for drug compounds, low rather than high hydrophobicity appears associated, albeit weakly, with promiscuous binding for the metabolite set investigated in this study. Across several physicochemical properties, drug compounds exhibit characteristic binding propensities that are distinguishable from those associated with metabolites. Prediction of target diversity and compound promiscuity using physicochemical properties was possible at modest accuracy levels only, but was consistently better for drugs than for metabolites. Compound properties capturing structural flexibility and hydrogen-bond formation descriptors proved most informative in PLS-based prediction models. With regard to diversity of enzymatic activities of the respective metabolite target enzymes, the metabolites benzylsuccinate, hypoxanthine, trimethylamine N-oxide, oleoylglycerol, and resorcinol showed very narrow process involvement, while glycine, imidazole, tryptophan, succinate, and glutathione were identified to possess broad enzymatic reaction scopes. Promiscuous metabolites were found to mainly serve as general energy currency compounds, but were identified to also be involved in signaling processes and to appear in diverse organismal systems (digestive and nervous system) suggesting specific molecular and physiological roles of promiscuous metabolites. PMID:26442281

Micellar electrokinetic chromatography with acid labile surfactant.

PubMed

Stanley, Bob; Lucy, Charles A

2012-02-24

We present a study of a degradable surfactant, sodium 4-[(2-methyl-2-undecyl-1,3-dioxolan-4-yl)methoxy]-1-propane sulfonate that is also known as an acid-labile surfactant (ALS). The performance of ALS as a pseudostationary phase is assessed and compared with established pseudostationary phases such as sodium dodecyl sulphate (SDS), volatile surfactants and polymeric micelles. ALS achieves separation efficiency of 100,000-145,000 theoretical plates and relative standard deviation (RSD) of electrophoretic mobility (n=5) of less than 3%. Retention factors with ALS are strongly correlated with those with SDS. This is shown by the R2=0.79 for all eleven analytes and an R2=0.992 for specifically the non-hydrogen bonding (NHB) analytes. However, ALS displays different selectivity than SDS for hydrogen bond donor (HBD) and hydrogen bond acceptor (HBA) solutes (R2 of 0.74 and 0.88, respectively). ALS is degraded to less surface active compounds in acidic solution. These less surface-active compounds are more compatible with the electrospray ionization mass spectrometry (ESI-MS). ALS has a half-life of 48 min at pH 4. ALS has the potential to couple micellar electrokinetic chromatography (MEKC) with the ESI-MS. ALS can be used as a pseudostationary phase for a high efficiency separation and later acid hydrolyzed to enable an ESI-MS analysis. Copyright © 2011 Elsevier B.V. All rights reserved.

Interactions of Enolizable Barbiturate Dyes.

PubMed

Schade, Alexander; Schreiter, Katja; Rüffer, Tobias; Lang, Heinrich; Spange, Stefan

2016-04-11

The specific barbituric acid dyes 1-n-butyl-5-(2,4-dinitro-phenyl) barbituric acid and 1-n-butyl-5-{4-[(1,3-dioxo-1H-inden-(3 H)-ylidene)methyl]phenyl}barbituric acid were used to study complex formation with nucleobase derivatives and related model compounds. The enol form of both compounds shows a strong bathochromic shift of the UV/Vis absorption band compared to the rarely coloured keto form. The keto-enol equilibria of the five studied dyes are strongly dependent on the properties of the environment as shown by solvatochromic studies in ionic liquids and a set of organic solvents. Enol form development of the barbituric acid dyes is also associated with alteration of the hydrogen bonding pattern from the ADA to the DDA type (A=hydrogen bond acceptor site, D=donor site). Receptor-induced altering of ADA towards DDA hydrogen bonding patterns of the chromophores are utilised to study supramolecular complex formation. As complementary receptors 9-ethyladenine, 1-n-butylcytosine, 1-n-butylthymine, 9-ethylguanidine and 2,6-diacetamidopiridine were used. The UV/Vis spectroscopic response of acid-base reaction compared to supramolecular complex formation is evaluated by (1)H NMR titration experiments and X-ray crystal structure analyses. An increased acidity of the barbituric acid derivative promotes genuine salt formation. In contrast, supramolecular complex formation is preferred for the weaker acidic barbituric acid. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Poly(1-allylimidazole)-grafted silica, a new specific stationary phase for reversed-phase and anion-exchange liquid chromatography.

PubMed

Sun, Min; Qiu, Hongdeng; Wang, Licheng; Liu, Xia; Jiang, Shengxiang

2009-05-01

A new specific stationary phase based on poly(1-allylimidazole)-grafted silica has been synthesized and characterized, by infrared spectra, elemental analysis, thermogravimetric analysis and X-ray photoelectron spectroscopy. The results of test showed that poly(1-allylimidazole) can effectively mask the residual silanol groups and reduce the adverse effect of residual silanol. Using this stationary phase, phenol compounds, aniline compounds, and polycyclic aromatic hydrocarbons were successfully separated with symmetric peak shapes in the reversed-phase chromatography. Inorganic anions (IO(3)(-), BrO(3)(-), Br(-), NO(3)(-), I(-), SCN(-)) were also separated completely in the anion-exchange chromatography using sodium chloride solution as the mobile phase. The effects of pH and the concentration of eluent on the separation of inorganic anions were studied. The separation mechanism appears to involve the mixed interactions of hydrogen bonding, hydrophobic, pi-pi, electrostatic, and anion-exchange interactions.

Impact of furan derivatives and phenolic compounds on hydrogen production from organic fraction of municipal solid waste using co-culture of Enterobacter aerogenes and E. coli.

PubMed

Sharma, Preeti; Melkania, Uma

2017-09-01

In the present study, the effect of furan derivatives (furfural and 5-hydroxymethylfurfural) and phenolic compounds (vanillin and syringaldehyde) on hydrogen production from organic fraction of municipal solid waste (OFMSW) was investigated using co-culture of facultative anaerobes Enterobacter aerogenes and E. coli. The inhibitors were applied in the concentration ranges of 0.25, 0.5, 1, 2 and 5g/L each. Inhibition coefficients of phenolic compounds were higher than those of furan derivatives and vanillin exhibited maximum inhibition coefficients correspondingly lowest hydrogen yield among all inhibitors. Furfural and 5-hydroxymethylfurfural addition resulted in an average decrease of 26.99% and 37.16% in hydrogen yield respectively, while vanillin and syringaldehyde resulted in 49.40% and 42.26% average decrease in hydrogen yield respectively. Further analysis revealed that Furfural and 5-hydroxymethylfurfural were completely degraded up to concentrations of 1g/L, while vanillin and syringaldehyde were degraded completely up to the concentration of 0.5g/L. Volatile fatty acid generation decreased with inhibitors addition. Copyright © 2017 Elsevier Ltd. All rights reserved.

Organic silicon compounds anf hydrogen sulfide removal from biogas by mineral and adsorbent

NASA Astrophysics Data System (ADS)

Choi, J.

2015-12-01

Biogas utilized for energy production needs to be free from organic silicon compounds and hydrogen sulfide , as their burning has damaging effects on utilities and humans; organic silicon compounds and hydrogen sulfide can be found in biogas produced from biomass wastes, due to their massive industrial use in synthetic product,such as cosmetics, detergents and paints.Siloxanes and hydrogen sulfide removal from biogas can be carried out by various methods (Ajhar et al., 2010); aim of the present work is to find a single practical andeconomic way to drastically and simultaneously reduce both hydrogen sulfide and the siloxanes concentration to less than 1 ppm. Some commercial activated carbons previously selected (Monteleoneet al., 2011) as being effective in hydrogen sulfide up taking have been tested in an adsorption measurement apparatus, by flowing both hydrogen sulphide and volatile siloxane (Decamethycyclopentasiloxane or D5) in a nitrogen stream,typically 25-300 ppm D5 over N2, through an clay minerals, Fe oxides and Silica; the adsorption process was analyzed by varying some experimental parameters (concentration, grain size, bed height). The best silica shows an adsorption capacity of 0.2 g D5 per gram of silica. The next thermo gravimetric analysis (TGA) confirms the capacity data obtained experimentally by the breakthrough curve tests.The capacity results depend on D5 and hydrogen sulphide concentrations. A regenerative silica process is then carried out byheating the silica bed up to 200 ° C and flushing out the adsorbed D5 and hydrogen sulphide samples in a nitrogen stream in athree step heating procedure up to 200 ° C. The adsorption capacity is observed to degrade after cyclingthe samples through several adsorption-desorption cycles.

Para-hydrogen induced polarization of Si-29 NMR resonances as a potentially useful tool for analytical applications.

PubMed

Ellena, Silvano; Viale, Alessandra; Gobetto, Roberto; Aime, Silvio

2012-08-01

Para-hydrogen-induced polarization effects have been observed in the (29)Si NMR spectra of trimethylsilyl para-hydrogenated molecules. The high signal enhancements and the long T(1) values observed for the (29)Si hyperpolarized resonances point toward the possibility of using (29)Si for hyperpolarization applications. A method for the discrimination of multiple compounds and/or complex mixtures of hydroxylic compounds (such as steroids), consisting of the silylization of alcoholic functionalities with an unsaturated silylalkyl moiety and subsequent reaction with para-H(2), is proposed. Copyright © 2012 John Wiley & Sons, Ltd.

Integrated coal liquefaction process

DOEpatents

Effron, Edward

1978-01-01

In a process for the liquefaction of coal in which coal liquids containing phenols and other oxygenated compounds are produced during the liquefaction step and later hydrogenated, oxygenated compounds are removed from at least part of the coal liquids in the naphtha and gas oil boiling range prior to the hydrogenation step and employed as a feed stream for the manufacture of a synthesis gas or for other purposes.

Chemical grafting of Co9S8 onto C60 for hydrogen spillover and storage.

PubMed

Han, Lu; Qin, Wei; Zhou, Jia; Jian, Jiahuang; Lu, Songtao; Wu, Xiaohong; Fan, Guohua; Gao, Peng; Liu, Boyu

2017-04-20

Metal modified C 60 is considered to be a potential hydrogen storage medium due to its high theoretical capacity. Research interest is growing in various hybrid inorganic compounds-C 60 . While the design and synthesis of a novel hybrid inorganic compound-C 60 is difficult to attain, it has been theorized that the atomic hydrogen could transfer from the inorganic compound to the adjacent C 60 surfaces via spillover and surface diffusion. Here, as a proof of concept experiment, we graft Co 9 S 8 onto C 60 via a facile high energy ball milling process. The Raman, XPS, XRD, TEM, HTEM and EELS measurements have been conducted to evaluate the composition and structure of the pizza-like hybrid material. In addition, the electrochemical measurements and calculated results demonstrate that the chemical "bridges" (C-S bonds) between these two materials enhance the binding strength and, hence, facilitate the hydriding reaction of C 60 during the hydrogen storage process. As a result, an increased hydrogen storage capacity of 4.03 wt% is achieved, along with a favorable cycling stability of ∼80% after 50 cycles. Excluding the direct hydrogen storage contribution from Co 9 S 8 in the hybrid paper, the hydrogen storage ability of C 60 was enhanced by 5.9× through the hydriding reaction caused by the Co 9 S 8 modifier. Based on these experimental measurements and theoretical calculations, the unique chemical structure reported here could potentially inspire other C 60 -based advanced hybrids.

Para-hydrogen perspectives in hyperpolarized NMR.

PubMed

Glöggler, Stefan; Colell, Johannes; Appelt, Stephan

2013-10-01

The first instance of para-hydrogen induced polarization (PHIP) in an NMR experiment was serendipitously observed in the 1980s while investigating a hydrogenation reaction (Seldler et al., 1983; Bowers and Weitekamp, 1986, 1987; Eisenschmid et al., 1987) [1-4]. Remarkably a theoretical investigation of the applicability of para-hydrogen as a hyperpolarization agent was being performed in the 1980's thereby quickly providing a theoretical basis for the PHIP-effect (Bowers and Weitekamp, 1986) [2]. The discovery of signal amplification by a non-hydrogenating interaction with para-hydrogen has recently extended the interest to exploit the PHIP effect, as it enables investigation of compounds without structural alteration while retaining the advantages of spectroscopy with hyperpolarized compounds [5]. In this article we will place more emphasis of the future applications of the method while only briefly discussing the efforts that have been made in the understanding of the phenomenon and the development of the method so far. Copyright © 2013 Elsevier Inc. All rights reserved.

Electrocatalytic hydrogenation and hydrodeoxygenation of oxygenated and unsaturated organic compounds

DOEpatents

Jackson, James E.; Lam, Chun Ho; Saffron, Christopher M.; Miller, Dennis J.

2018-04-24

A process and related electrode composition are disclosed for the electrocatalytic hydrogenation and/or hydrodeoxygenation of organic substrates such as biomass-derived bio-oil components by the production of hydrogen atoms on a catalyst surface followed by the reaction of the hydrogen atoms with the organic reactants. Biomass fast pyrolysis-derived bio-oil is a liquid mixture containing hundreds of organic compounds with chemical functionalities that are corrosive to container materials and are prone to polymerization. A high surface area skeletal metal catalyst material such as Raney Nickel can be used as the cathode. Electrocatalytic hydrogenation and/or hydrodeoxygenation convert the organic substrates under mild conditions to reduce coke formation and catalyst deactivation. The process converts oxygen-containing functionalities and unsaturated bonds into chemically reduced forms with an increased hydrogen content. The process is operated at mild conditions, which enables it to be a good means for stabilizing bio-oil to a form that can be stored and transported using metal containers and pipes.

A Compound-Specific Hydrogen Isotope Record at the Onset of Ocean Anoxic Event 2, Kaiparowits Plateau, Southern Utah

NASA Astrophysics Data System (ADS)

Todes, J.; Jones, M. M.; Sageman, B. B.; Osburn, M. R.

2017-12-01

Rhythmic lithologic variations (limestone-shale couplets) interpreted to reflect Milankovitch cycles occur at the onset of Ocean Anoxic Event 2 (OAE2) in deposits of the Western Interior Seaway. These couplets have been interpreted to reflect climate cycles: however, the physical mechanism(s) through which climate cycles were translated to the sedimentary record during peak greenhouse conditions remain unsettled. Although glacioeustasy has been considered, variance in surface ocean temperature, ocean circulation, or local hydrology may be more plausible options. Compound-specific hydrogen isotope ratios (δ2H) of n-alkanes and other biomarkers may provide a means to evaluate such mechanisms. Since sedimentary alkanes are direct products of plants and membrane lipid diagenesis and are resistant to secondary hydrogen exchange during thermal maturation at low (<100 oC) temperatures, they have the potential to reflect the isotopic composition of primary waters. The Tropic Shale of the Kaiparowits Plateau (Southern Utah) provides an exceptional opportunity to explore δ2H variability in this interval. Outcrop samples of three couplets have been extracted, separated, and analyzed to ascertain facies-specific δ2H variability. Strong odd-over-even n-alkane chain length distributions suggest low thermal maturity and the possible preservation of primary δ2H values. Short and long chain ­n-alkanes are potentially sourced from planktonic biomass and terrestrial plants, respectively, enabling a comparison of climatic processes between marine and terrestrial settings. Biomarkers, including both steranes and hopanes, are also preserved and reflect putative source organisms and local paleoenvironmental conditions. Facies-specific δ2H analysis will allow for evaluation of changes in the dominant source of atmospheric moisture in the Western Interior during orbitally-forced climate cycles. Organic matter deposited during periods of northerly Boreal influence would have a depleted 2H-isotope composition relative to those deposited during periods of more southerly Tethys influence. In this model, these variations are reflected by lithology - limestone deposition would occur during warm, evaporative Tethys-dominated times, while cooler, wetter Boreal periods would promote shale deposition.

Mediating chemical reactions using polysaccharides

NASA Astrophysics Data System (ADS)

Tyler, Lauren E.

We have studied the NaBH4-mediated hydrogenation of select alkenes catalyzed by polysaccharide-stabilized nanoparticles. We compared the catalytic properties of Ni-based nanoparticles or Au/Co-based nanoparticles on the hydrogenation of cinnamic acid, cinnamide, cinnamyl alcohol, and ethyl cinnamate. We evaluated the possibility that the type of stabilizing polysaccharide surrounding the nanoparticle may affect the selectivity towards the alkene compounds that undergo the hydrogenation reaction. We found that the hydrogenation of cinnamide or ethyl cinnamate proceeded readily to 100% completion independent of the type of polysaccharide stabilizing the nanoparticle. However, the extent of the hydrogenation of cinnamyl alcohol and cinnamic acid varied greatly depending on the type of polysaccharide stabilizing the nanoparticle. In the course of these studies, we observed that some polysaccharides by themselves promoted the hydrolysis of ethyl cinnamate. Thus, we have raised the hypothesis that some polysaccharides may act as "esterases" and explored the interaction between select polysaccharides and a variety of ester compounds.

Hydrogen Isotope Measurements of Organic Acids and Alcohols by Pyrolysis-GC-MS-TC-IRMS

NASA Technical Reports Server (NTRS)

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

2011-01-01

One possible process responsible for methane generation on Mars is abiotic formation by Fischer-Tropsch-type (FTT) synthesis during serpentinization reactions. Measurement of carbon and hydrogen isotopes of intermediary organic compounds can help constrain the origin of this methane by tracing the geochemical pathway during formation. 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 hydrogen isotope measurements. Reported here are results of experiments to characterize the hydrogen isotope composition of low molecular weight organic acids and alcohols. The presence of these organic compounds has been suggested by others as intermeadiary products made during mineral surface catalyzed reactions. This work compliments our previous study characterizing the carbon isotope composition of similar low molecular weight intermediary organic compounds (Socki, et al, American Geophysical Union Fall meeting, Abstr. #V51B-2189, Dec., 2010). Our hydrogen isotope measurements utilize a unique analytical technique combining Pyrolysis-Gas Chromatograph-Mass Spectrometry-High Temperature Conversion-Isotope Ratio Mass Spectrometry (Py-GC-MS-TC-IRMS). Our technique is unique 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 separated organic compounds, therefore both chemical and isotopic measurements can be carried out simultaneously on the same sample.

Water cavities of sH clathrate hydrate stabilized by molecular hydrogen.

PubMed

Strobel, Timothy A; Koh, Carolyn A; Sloan, E Dendy

2008-02-21

X-ray diffraction and Raman spectroscopic measurements confirm that molecular hydrogen can be contained within the small water cavities of a binary sH clathrate hydrate using large guest molecules that stabilize the large cavity. The potential increase in hydrogen storage could be more than 40% when compared with binary sII hydrates. This work demonstrates the stabilization of hydrogen in a hydrate structure previously unknown for encapsulating molecular hydrogen, indicating the potential for other inclusion compound materials with even greater hydrogen storage capabilities.

Thermodynamical properties of La-Ni-T (T = Mg, Bi and Sb) hydrogen storage systems

NASA Astrophysics Data System (ADS)

Giza, K.; Iwasieczko, W.; Pavlyuk, V. V.; Bala, H.; Drulis, H.

The hydrogen absorption properties of LaNi 4.8T 0.2 (T = Mg, Bi and Sb) alloys are reported. The effects of the substitution of Ni in the LaNi 5 compound with Mg, Bi and Sb are investigated. The ability of alloys to absorb hydrogen is characterized by the pressure-composition (p- c) isotherms. The p- c isotherms allow the determining thermodynamic parameters enthalpy (Δ H des) and entropy (Δ S des) of the dehydrogenation processes. The calculated Δ H des and Δ S des data helps to explain the decrease of hydrogen equilibrium pressure in alloys doped with Al, Mg and Bi and its increase in the Sb-doped LaNi 5 compound. Generally, partial substitution of Ni in LaNi 5 compound with Mg, Bi and Sb cause insignificant changes of hydrogen storage capacity compared to the hydrogen content in the initial LaNi 5H 6 hydride phase. However, it is worth to stress that, in the case of LaNi 4.8Bi 0.2, a small increase of H/f.u. up to 6.8 is observed. The obtained results in these investigations indicate that the LaNi 4.8T 0.2 (T = Al, Mg and Bi) alloys can be very attractive materials dedicated for negative electrodes in Ni/MH batteries.

Hydrogenation of biomass-derived substrates

DOEpatents

Gordon, John C.; Waidmann, Christopher R.

2016-06-07

The .alpha.,.beta.-unsaturated ketone moiety of a substrate representative of non-food based biomass was hydrogenated to the corresponding saturated alcohol moiety using a composition including (1) a copper salt; (2) a phosphine; (3) a polar aprotic solvent such as acetonitrile, and (4) a compound suitable for providing hydrogen for the hydrogenation, such as a suitable silane material or a suitable siloxane material.

Quantitative on-line analysis of sulfur compounds in complex hydrocarbon matrices.

PubMed

Djokic, Marko R; Ristic, Nenad D; Olahova, Natalia; Marin, Guy B; Van Geem, Kevin M

2017-08-04

An improved method for on-line measurement of sulfur containing compounds in complex matrices is presented. The on-line system consists of a specifically designed sampling system connected to a comprehensive two-dimensional gas chromatograph (GC×GC) equipped with two capillary columns (Rtx ® -1 PONA×SGE BPX50), a flame ionization detector (FID) and a sulfur chemiluminescence detector (SCD). The result is an unprecedented sensitivity down to ppm level (1 ppm-w) for various sulfur containing compounds in very complex hydrocarbon matrices. In addition to the GC×GC-SCD, the low molecular weight sulfur containing compounds such as hydrogen sulfide (H 2 S) and carbonyl sulfide (COS) can be analyzed using a thermal conductivity detector of a so-called refinery gas analyzer (RGA). The methodology was extensively tested on a continuous flow pilot plant for steam cracking, in which quantification of sulfur containing compounds in the reactor effluent was carried out using 3-chlorothiophene as internal standard. The GC×GC-FID/-SCD settings were optimized for ppm analysis of sulfur compounds in olefin-rich (ethylene- and propylene-rich) hydrocarbon matrices produced by steam cracking of petroleum feedstocks. Besides that is primarily used for analysis of the hydrocarbon matrix, FID of the GC×GC-FID/-SCD set-up serves to double check the amount of added sulfur internal standard which is crucial for a proper quantification of sulfur compounds. When vacuum gas oil containing 780 ppm-w of elemental sulfur in the form of benzothiophenes and dibenzothiophenes is subjected to steam cracking, the sulfur balance was closed, with 75% of the sulfur contained in the feed is converted to hydrogen sulfide, 13% to alkyl homologues of thiophene while the remaining 12% is present in the form of alkyl homologues of benzothiophenes. The methodology can be applied for many other conversion processes which use sulfur containing feeds such as hydrocracking, catalytic cracking, kerogen evolution, bio-waste pyrolysis, supercritical water treatment, etc. Copyright © 2017 Elsevier B.V. All rights reserved.

Compound-specific carbon, nitrogen, and hydrogen isotopic ratios for amino acids in CM and CR chondrites and their use in evaluating potential formation pathways

NASA Astrophysics Data System (ADS)

Elsila, Jamie E.; Charnley, Steven B.; Burton, Aaron S.; Glavin, Daniel P.; Dworkin, Jason P.

2012-09-01

Stable hydrogen, carbon, and nitrogen isotopic ratios (δD, δ13C, and δ15N) of organic compounds can reveal information about their origin and formation pathways. Several formation mechanisms and environments have been postulated for the amino acids detected in carbonaceous chondrites. As each proposed mechanism utilizes different precursor molecules, the isotopic signatures of the resulting amino acids may indicate the most likely of these pathways. We have applied gas chromatography with mass spectrometry and combustion isotope ratio mass spectrometry to measure the compound-specific C, N, and H stable isotopic ratios of amino acids from seven CM and CR carbonaceous chondrites: CM1/2 Allan Hills (ALH) 83100, CM2 Murchison, CM2 Lewis Cliff (LEW) 90500, CM2 Lonewolf Nunataks (LON) 94101, CR2 Graves Nunataks (GRA) 95229, CR2 Elephant Moraine (EET) 92042, and CR3 Queen Alexandra Range (QUE) 99177. We compare the isotopic compositions of amino acids in these meteorites with predictions of expected isotopic enrichments from potential formation pathways. We observe trends of decreasing δ13C and increasing δD with increasing carbon number in the α-H, α-NH2 amino acids that correspond to predictions made for formation via Strecker-cyanohydrin synthesis. We also observe light δ13C signatures for β-alanine, which may indicate either formation via Michael addition or via a pathway that forms primarily small, straight-chain, amine-terminal amino acids (n-ω-amino acids). Higher deuterium enrichments are observed in α-methyl amino acids, indicating formation of these amino acids or their precursors in cold interstellar or nebular environments. Finally, individual amino acids are more enriched in deuterium in CR chondrites than in CM chondrites, reflecting different parent-body chemistry.

Compound-Specific Carbon, Nitrogen, and Hydrogen Isotopic Ratios for Amino Acids in CM and CR Chondrites and their use in Evaluating Potential Formation Pathways

NASA Technical Reports Server (NTRS)

Elsila, Jamie E.; Charnley, Steven B.; Burton, Aaron S.; Glavin, Daniel P.; Dworkin, Jason P.

2012-01-01

Stable hydrogen, carbon, and nitrogen isotopic ratios (oD, 013C, and olSN) of organic compounds can revcal information about their origin and formation pathways. Several formation mechanisms and environments have been postulated for the amino acids detected in carbonaceous chondrites. As each proposed mechanism utilizes different precursor molecules, the isotopic signatures of the resulting amino acids may indicate the most likely of these pathways. We have applied gas chromatography with mass spectrometry and combustion isotope ratio mass spectrometry to measure the compound-specific C, N, and H stable isotopic ratios of amino acids from seven CM and CR carbonaceous chondrites: CM1I2 Allan Hills (ALH) 83100, CM2 Murchison, CM2 Lewis Cliff (LEW) 90500, CM2 Lonewolf Nunataks (LON) 94101, CRZ Graves Nunataks (GRA) 95229, CRZ Elephant Moraine (EET) 92042, and CR3 Queen Alexandra Range (QUE) 99177. We compare the isotopic compositions of amino acids in these meteorites with predictions of expected isotopic enrichments from potential formation pathways. We observe trends of decreasing ODC and increasing oD with increasing carbon number in the aH, (l-NH2 amino acids that correspond to predictions made for formation via Streckercyanohydrin synthesis. We also observe light ODC signatures for -alanine, which may indicate either formation via Michael addition or via a pathway that forms primarily small, straight-chain, amine-terminal amino acids (n-ro-amino acids). Higher deuterium enrichments are observed in amethyl amino acids, indicating formation of these amino acids or their precursors in cold interstellar or nebular environments. Finally, individual amino acids are more enriched in deuterium in CR chondrites than CM chondrites, reflecting different parent-body chemistry.

Models for liquid-liquid partition in the system dimethyl sulfoxide-organic solvent and their use for estimating descriptors for organic compounds.

PubMed

Karunasekara, Thushara; Poole, Colin F

2011-07-15

Partition coefficients for varied compounds were determined for the organic solvent-dimethyl sulfoxide biphasic partition system where the organic solvent is n-heptane or isopentyl ether. These partition coefficient databases are analyzed using the solvation parameter model facilitating a quantitative comparison of the dimethyl sulfoxide-based partition systems with other totally organic partition systems. Dimethyl sulfoxide is a moderately cohesive solvent, reasonably dipolar/polarizable and strongly hydrogen-bond basic. Although generally considered to be non-hydrogen-bond acidic, analysis of the partition coefficient database strongly supports reclassification as a weak hydrogen-bond acid in agreement with recent literature. The system constants for the n-heptane-dimethyl sulfoxide biphasic system provide an explanation of the mechanism for the selective isolation of polycyclic aromatic compounds from mixtures containing low-polarity hydrocarbons based on the capability of the polar interactions (dipolarity/polarizability and hydrogen-bonding) to overcome the opposing cohesive forces in dimethyl sulfoxide that are absent for the interactions with hydrocarbons of low polarity. In addition, dimethyl sulfoxide-organic solvent systems afford a complementary approach to other totally organic biphasic partition systems for descriptor measurements of compounds virtually insoluble in water. Copyright © 2011 Elsevier B.V. All rights reserved.

Hydrolysis of Mg(BH4)2 and its coordination compounds as a way to obtain hydrogen

NASA Astrophysics Data System (ADS)

Solovev, Mikhail V.; Chashchikhin, Oleg V.; Dorovatovskii, Pavel V.; Khrustalev, Victor N.; Zyubin, A. S.; Zyubina, T. S.; Kravchenko, O. V.; Zaytsev, Alexey A.; Dobrovolsky, Yu. A.

2018-02-01

Three ligand-stabilized Mg(BH4)2-based complexes have been synthesized and evaluated as potential hydrogen storage media for portable fuel cell applications. The new borohydrides: Mg(BH4)2 × 0.5Et2O and Mg(BH4)2 × diglyme (diglyme - CH3O(CH2)2O(CH2)2OCH3) have been synthesized and examined by X-ray single crystal diffraction method. Hydrolysis reactions of the compounds liberate hydrogen in quantities ranging from 46 to 96% of the theoretical yield. The hydrolysis of Mg(BH4)2 and other borohydrides is also accompanied by the diborane formation. The amount of liberated diborane depends on the Mg-coordination environment. To explain this fact quantum-chemical calculations have been performed. It is shown that formation of Mg-O-Mg-bridges enables the side process of diborane generation. It means that the size and denticity of the ligand directly affects the amount of released diborane. In general, the larger the ligand and the higher its denticity, the smaller is amount of diborane produced. The new compound Mg(BH4)2 × diglyme decomposes without diborane formation that allows one to be considered as a new promising chemical hydrogen storage compound for the practical usage.

Hydrogen bonding. Part 25. The nature of the hydrogen bond in hydroxytropenylium chloride (tropone hydrochloride)

NASA Astrophysics Data System (ADS)

Harmon, Kenneth M.; Cross, Joan E.; Toccalino, Patricia L.

1988-08-01

Hydroxytropenylium iodide and bromide contain normal electrostatic OH⋯X - hydrogen bonds. Hydroxytropenylium chloride, however, contains a hydrogen bond intermediate between the normal electrostatic type and the very strong covalent type, similar to the hydrogen bonds found in choline fluoride or the Type I C∞v hydrogen dihalide ions. Infrared comparisons with compounds previously studied demonstrate that the hydroxytropenylium ion is a stronger hydrogen bond donor than either choline cation or protonated betaine cation, and suggest that hydroxytropenylium fluoride, if it can be prepared, should contain a three-center covalent hydrogen bond.

Polymer blend compositions and methods of preparation

DOEpatents

Naskar, Amit K.

2016-09-27

A polymer blend material comprising: (i) a first polymer containing hydrogen bond donating groups having at least one hydrogen atom bound to a heteroatom selected from oxygen, nitrogen, and sulfur, or an anionic version of said first polymer wherein at least a portion of hydrogen atoms bound to a heteroatom is absent and replaced with at least one electron pair; (ii) a second polymer containing hydrogen bond accepting groups selected from nitrile, halogen, and ether functional groups; and (iii) at least one modifying agent selected from carbon particles, ether-containing polymers, and Lewis acid compounds; wherein, if said second polymer contains ether functional groups, then said at least one modifying agent is selected from carbon particles and Lewis acid compounds. Methods for producing the polymer blend, molded forms thereof, and articles thereof, are also described.

Catalytic biomass conversion methods, catalysts, and methods of making the same

DOEpatents

Delgass, William Nicholas; Agrawal, Rakesh; Ribeiro, Fabio Henrique; Saha, Basudeb; Yohe, Sara Lynn; Abu-Omar, Mahdi M; Parsell, Trenton; Dietrich, Paul James; Klein, Ian Michael

2017-10-10

Described herein are processes for one-step delignification and hydrodeoxygenation of lignin fraction a biomass feedstock. The lignin feedstock is derived from by-products of paper production and biorefineries. Additionally described is a process for converting biomass-derived oxygenates to lower oxygen-content compounds and/or hydrocarbons in the liquid or vapor phase in a reactor system containing hydrogen and a catalyst comprised of a hydrogenation function and/or an oxophilic function and/or an acid function. Finally, also described herein is a process for converting biomass-derived oxygenates to lower oxygen-content compounds and/or hydrocarbons in the liquid or vapor phase in a reactor system containing hydrogen and a catalyst comprised of a hydrogenation function and/or an oxophilic function and/or an acid function.

Photochemical processes on Titan: Irradiation of mixtures of gases that simulate Titan's atmosphere

NASA Astrophysics Data System (ADS)

Tran, Buu N.; Joseph, Jeffrey C.; Force, Michael; Briggs, Robert G.; Vuitton, Veronique; Ferris, James P.

2005-09-01

Photochemical reaction pathways in Titan's atmosphere were investigated by irradiation of the individual components and the mixture containing nitrogen, methane, hydrogen, acetylene, ethylene, and cyanoacetylene. The quantum yields for the loss of the reactants and the formation of products were determined. Photolysis of ethylene yields mainly saturated compounds (ethane, propane, and butane) while photolysis of acetylene yields the same saturated compounds as well as ethylene and diacetylene. Irradiation of cyanoacetylene yields mainly hydrogen cyanide and small amounts of acetonitrile. When an amount of methane corresponding to its mixing ratio on Titan was added to these mixtures the quantum yields for the loss of reactants decreased and the quantum yields for hydrocarbon formation increased indicative of a hydrogen atom abstraction from methane by the photochemically generated radicals. GC/MS analysis of the products formed by irradiation of mixtures of all these gases generated over 120 compounds which were mainly aliphatic hydrocarbons containing double and triple bonds along with much smaller amounts of aromatic compounds like benzene, toluene and phenylacetylene. The reaction pathways were investigated by the use of 13C acetylene in these gas mixtures. No polycyclic aromatic compounds were detected. Vapor pressures of these compounds under conditions present in Titan's atmosphere were calculated. The low molecular weight compounds likely to be present in the atmosphere and aerosols of Titan as a result of photochemical processes are proposed.

Synthesis of novel benzohydrazone-oxadiazole hybrids as β-glucuronidase inhibitors and molecular modeling studies.

PubMed

Taha, Muhammad; Ismail, Nor Hadiani; Imran, Syahrul; Selvaraj, Manikandan; Rahim, Abdul; Ali, Muhammad; Siddiqui, Salman; Rahim, Fazal; Khan, Khalid Mohammed

2015-12-01

A series of compounds consisting of 25 novel oxadiazole-benzohydrazone hybrids (6-30) were synthesized through a five-step reaction sequence and evaluated for their β-glucuronidase inhibitory potential. The IC50 values of compounds 6-30 were found to be in the range of 7.14-44.16μM. Compounds 6, 7, 8, 9, 11, 13, 18, and 25 were found to be more potent than d-saccharic acid 1,4-lactone (48.4±1.25μM). These compounds were further subjected for molecular docking studies to confirm the binding mode towards human β-d-glucuronidase active site. Docking study for compound 13 (IC50=7.14±0.30μM) revealed that it adopts a binding mode that fits within the entire pocket of the binding site of β-d-glucuronidase. Compound 13 has the maximum number of hydrogens bonded to the residues of the active site as compared to the other compounds, that is, the ortho-hydroxyl group forms hydrogen bond with carboxyl side chain of Asp207 (2.1Å) and with hydroxyl group of Tyr508 (2.6Å). The other hydroxyl group forms hydrogen bond with His385 side chain (2.8Å), side chain carboxyl oxygen of Glu540 (2.2Å) and Asn450 side-chain's carboxamide NH (2.1Å). Copyright © 2015 Elsevier Ltd. All rights reserved.

Oxygen stabilized zirconium-vanadium-iron alloy

DOEpatents

Mendelsohn, Marshall H.; Gruen, Dieter M.

1982-01-01

An oxygen stabilized intermetallic compound having the formula (Zr.sub.1-x Ti.sub.x).sub.2-u (V.sub.1-y Fe.sub.y)O.sub.z where x=0.0 to 0.9, y=0.01 to 0.9, z=0.25 to 0.5 and u=0 to 1. The compound is capable of reversibly sorbing hydrogen at temperatures from -196.degree. C. to 200.degree. C. at pressures down to 10.sup.-6 torr. The compound is suitable for use as a hydrogen getter in low pressure, high temperature applications such as magnetic confinement fusion devices.

Oxygen-stabilized zirconium-vanadium-iron alloy

DOEpatents

Mendelsohn, M.H.; Gruen, D.M.

1981-06-16

An oxygen stabilized intermetallic compound is described which has the formula (Zr/sub 1-x/Ti/sub x/)/sub 2-u/(V/sub 1-y/Fe/sub y/)O/sub z/ where x = 0.0 to 0.9, y = 0.01 to 0.9, z = 0.25 to 0.5 and u = 0 to 1. The compound is capable of reversibly sorbing hydrogen at temperatures from -196/sup 0/C to 200/sup 0/C at pressures down to 10/sup -6/ torr. The compound is suitable for use as a hydrogen getter in low pressure, high temperature applications such as magnetic confinement fusion devices.

Biodegradation of PCE and TCE in landfill leachate predicted from concentrations of molecular hydrogen: a case study.

PubMed

Gonsoulin, Mary E; Wilson, Barbara H; Wilson, John T

2004-12-01

The Refuse Hideaway Landfill (23-acre) received municipal, commercial, and industrial waste between 1974 and 1988. It was designed as a "natural attenuation" landfill and no provision was made to collect and treat contaminated water. Natural biological degradation through sequential reductive dechlorination had been an important mechanism for natural attenuation at the site. We used the concentration of hydrogen to forecast whether reductive dechlorination would continue over time at particular locations in the plume. Based on published literature, reductive dechlorination and natural attenuation of PCE, TCE, and cis-DCE can be expected in the aquifer if the concentration of molecular hydrogen in monitoring wells are adequate (> 1 nanomolar). Reductive dechlorination can be expected to continue as the ground water moves down gradient. Natural attenuation through reductive dechlorination is not expected in flow paths that originate at down gradient monitoring wells with low concentrations of molecular hydrogen (< 1 nanomolar). In three monitoring wells at the margin of the landfill and in five monitoring wells down gradient of the landfill, ground water maintained a molecular hydrogen concentration, ranging from 1.30 to 9.17 nanomolar, that is adequate for reductive dechlorination. In three of the monitoring wells far down gradient of the landfill, the concentration of molecular hydrogen (0.33 to 0.83 nanomolar) was not adequate to support reductive dechlorination. In wells with adequate concentrations of hydrogen, the concentrations of chlorinated volatile organic compounds were attenuated over time, or concentrations of chlorinated volatile organics were below the detection limit. In wells with inadequate concentrations of hydrogen, the concentrations of chlorinated organic compounds attenuated at a slower rate over time. In wells with adequate hydrogen the first order rate of attenuation of PCE, TCE, cis-DCE and total chlorinated volatile organic compounds varies from 0.38 to 0.18 per year. In wells without adequate hydrogen the rate varies from 0.015 to 0.006 per year.

Two-dimensional gas chromatography-online hydrogenation for improved characterization of petrochemical samples.

PubMed

Potgieter, H; Bekker, R; Govender, A; Rohwer, E

2016-05-06

The Fischer-Tropsch (FT) process produces a variety of hydrocarbons over a wide carbon number range and during subsequent product workup a large variety of synthetic fuels and chemicals are produced. The complexity of the product slate obtained from this process is well documented and the high temperature FT (HT-FT) process products are spread over gas, oil and water phases. The characterization of these phases is very challenging even when using comprehensive two-dimensional gas chromatography time-of-flight mass spectrometry (GC×GC-TOFMS). Despite the increase in separation power, peak co-elution still occurs when samples containing isomeric compounds are analysed by comprehensive two dimensional GC. The separation of isomeric compounds with the same double bond equivalents is especially difficult since these compounds elute in a similar position on the GC×GC chromatogram and have identical molecular masses and similar fragmentation patterns in their electron ionization (EI) mass spectra. On-line hydrogenation after GC×GC separation is a possible way to distinguish between these isomeric compounds since the number of rings and alkene double bonds can be determined from the mass spectra of the compounds before and after hydrogenation. This paper describes development of a GC×GC method with post column hydrogenation for the determination of the backbone of cyclic/olefinic structures enabling us to differentiate between classes like dienes and cyclic olefins in complex petrochemical streams. Copyright © 2016 Elsevier B.V. All rights reserved.

Molecular Dynamics Simulation of Mahkota Dewa (Phaleria Macrocarpa) Extract in Subcritical Water Extraction Process

NASA Astrophysics Data System (ADS)

Hashim, N. A.; Mudalip, S. K. Abdul; Harun, N.; Che Man, R.; Sulaiman, S. Z.; Arshad, Z. I. M.; Shaarani, S. M.

2018-05-01

Mahkota Dewa (Phaleria Macrocarpa), a good source of saponin, flavanoid, polyphenol, alkaloid, and mangiferin has an extensive range of medicinal effects. The intermolecular interactions between solute and solvents such as hydrogen bonding considered as an important factor that affect the extraction of bioactive compounds. In this work, molecular dynamics simulation was performed to elucidate the hydrogen bonding exists between Mahkota Dewa extracts and water during subcritical extraction process. A bioactive compound in the Mahkota Dewa extract, namely mangiferin was selected as a model compound. The simulation was performed at 373 K and 4.0 MPa using COMPASS force field and Ewald summation method available in Material Studio 7.0 simulation package. The radial distribution functions (RDF) between mangiferin and water signify the presence of hydrogen bonding in the extraction process. The simulation of the binary mixture of mangiferin:water shows that strong hydrogen bonding was formed. It is suggested that, the intermolecular interaction between OH2O••HMR4(OH1) has been identified to be responsible for the mangiferin extraction process.

(MnH9)2- salts with high hydrogen contents and unusual bonding: Density functional calculations

NASA Astrophysics Data System (ADS)

Gupta, Michèle; Gupta, Raju P.; Singh, D. J.

2009-12-01

The compounds BaReH9 and K2ReH9 are the prototypical members of a family of hydrides described as salts of (ReH9)2- anions. The structures reflect highly unusual chemistry with short H-H distances and at the same time very high ninefold coordination of Re by hydrogen atoms. This is of interest because of the resulting high hydrogen-to-metal ratios, 4.5 in BaReH9 and 3 in K2ReH9 . Here we use density functional calculations to investigate possible new members of this family including both Re and Mn compounds. We find that although SrReH9 and CaReH9 have not been synthesized these are very likely to be stable compounds that may be prepared in a similar manner as the Ba analog. We also find that the manganese counterparts, including K2MnH9 , are also likely to be stable and have thermodynamic properties consistent with requirements for hydrogen storage.

Oxidation of Molecular Hydrogen by a Chemolithoautotrophic Beggiatoa Strain

PubMed Central

2016-01-01

ABSTRACT A chemolithoautotrophic strain of the family Beggiatoaceae, Beggiatoa sp. strain 35Flor, was found to oxidize molecular hydrogen when grown in a medium with diffusional gradients of oxygen, sulfide, and hydrogen. Microsensor profiles and rate measurements suggested that the strain oxidized hydrogen aerobically when oxygen was available, while hydrogen consumption under anoxic conditions was presumably driven by sulfur respiration. Beggiatoa sp. 35Flor reached significantly higher biomass in hydrogen-supplemented oxygen-sulfide gradient media, but hydrogen did not support growth of the strain in the absence of reduced sulfur compounds. Nevertheless, hydrogen oxidation can provide Beggiatoa sp. 35Flor with energy for maintenance and assimilatory purposes and may support the disposal of internally stored sulfur to prevent physical damage resulting from excessive sulfur accumulation. Our knowledge about the exposure of natural populations of Beggiatoaceae to hydrogen is very limited, but significant amounts of hydrogen could be provided by nitrogen fixation, fermentation, and geochemical processes in several of their typical habitats such as photosynthetic microbial mats and submarine sites of hydrothermal fluid flow. IMPORTANCE Reduced sulfur compounds are certainly the main electron donors for chemolithoautotrophic Beggiatoaceae, but the traditional focus on this topic has left other possible inorganic electron donors largely unexplored. In this paper, we provide evidence that hydrogen oxidation has the potential to strengthen the ecophysiological plasticity of Beggiatoaceae in several ways. Moreover, we show that hydrogen oxidation by members of this family can significantly influence biogeochemical gradients and therefore should be considered in environmental studies. PMID:26896131

Structure and diffusion of furans and other cellulose-derived compounds in solvents via MD simulation

NASA Astrophysics Data System (ADS)

Rabideau, Brooks; Ismail, Ahmed

2011-03-01

There is now a large push towards the development of energy sources that are both environmentally friendly and sustainable; with the conversion of cellulose derived from biomass into biofuels being one promising route. In this conversion, a variety of intermediary compounds have been identified, which appear critical to successful expansion of the process to an industrial scale. Here we examine the structure and diffusion of these furans and acids derived from cellulose within ionic liquids via molecular dynamic simulation. Ionic liquids have shown the ability to dissolve cellulose with certain `green' benefits over existing, conventional solvents. Specifically, we study the solvation properties of these chemicals by examining the pair correlation functions of solute with solvent, and by exploring the agglomeration and separation of these chemicals from the solvent as well as the hydrogen bonding between species. Additionally, we determine the diffusion constant of these compounds in ionic liquid and aqueous solvents.

Qualitative and quantitative analysis of mixtures of compounds containing both hydrogen and deuterium

NASA Technical Reports Server (NTRS)

Crespi, H. L.; Harkness, L.; Katz, J. J.; Norman, G.; Saur, W.

1969-01-01

Method allows qualitative and quantitative analysis of mixtures of partially deuterated compounds. Nuclear magnetic resonance spectroscopy determines location and amount of deuterium in organic compounds but not fully deuterated compounds. Mass spectroscopy can detect fully deuterated species but not the location.

PERFLUORINATED AROMATIC COMPOUND

DTIC Science & Technology

octafluorobiphenyl, and perfluoroaliphatic aldehydes. Synthetic routes to perfluoro cyclohexyls via reactions of phenyl and pentafluorphenyl lithium with...other perfluorinated aromatic compounds were employed in the synthesis of perfluorinated aromatic model compounds and polymers. The hydrogenic analogues...hydrazides, and imides. Synthetic routes to perfluoro aralkyl compounds are being investigated. Starting materials are tetrafluorobenzene

Application of GC/MS Soft Ionization for Isomeric Biological Compound Analysis.

PubMed

Furuhashi, Takeshi; Okuda, Koji

2017-09-03

Isomers are compounds with the same molecular formula. Many different types of isomers are ubiquitous and play important roles in living organisms. Despite their early discovery, the actual analysis of isomers has been tricky and has confounded researchers. Using mass spectrometry (MS) to distinguish or identify isomers is an emergent topic and challenge for analytical chemists. We review some techniques for analyzing isomers with emphasis on MS, e.g., the roles of ion reaction, hydrogen-deuterium exchange, ion mobility mass spectrometry, ion spectroscopy, and energy change in producing isomer-specific fragments. In particular, soft ionization for gas chromatography-mass spectrometry (GC-MS) is a focus in this review. Awareness of the advantages and technical problems of these techniques would inspire innovation in future approaches.

Hydrothermal synthesis and characterization of a novel supramolecular network compound of Co(NIA) 2(H 2O) 4 with molecular ladder hydrogen bond chains (NIA=nicotinate)

NASA Astrophysics Data System (ADS)

Jia, Hong-Bin; Yu, Jie-Hui; Xu, Ji-Qing; Ye, Ling; Ding, Hong; Jing, Wei-Jie; Wang, Tie-Gang; Xu, Jia-Ning; Li, Zeng-Chun

2002-10-01

By hydrothermal method, a novel supramolecular compound, Co(NIA) 2(H 2O) 4 was synthesized and its structure was characterized with elemental analysis, FT-IR spectrum, TGA and X-ray diffractometer, indicating that it is a novel polyporous supramolecule with molecular ladder hydrogen-bonded chains. TGA curve shows its thermal stability up to 520 °C.

Chemical Reactions and Properties of Organosilicon Compounds Related to New Materials.

DTIC Science & Technology

1985-10-31

out. The compound behaves like an olefin in some reactions, for in- stance addition of hydrogen halides or chlorine: C1 2 HCI Mes 2 SiCl-SiClMes2...polymers have been synthesized which contain some silicon atoms bonded to hydrogen . These become crosslinked when mixed with substances containing several...and highly efficient catalysts, very small amounts are required in this process. Moreover, photocatalysis using polysilanes produces polymers with

Zirconium vanadium chromium alloy

DOEpatents

Mendelsohn, M.H.; Gruen, D.M.

1980-10-14

A ternary intermetallic compound having the formula Zr(V/sub 1-x/Cr/sub x/)/sub 2/ where x is in the range of 0.01 to 0.90 is capable of reversibly sorbing hydrogen at temperatures ranging from room temperature to 200/sup 0/C, at pressures down to 10/sup -6/ torr. The compound is suitable for use as a hydrogen getter in low pressure, high temperature applications such as magnetic confinement fusion devices.

High energy chemical laser system

DOEpatents

Gregg, D.W.; Pearson, R.K.

1975-12-23

A high energy chemical laser system is described wherein explosive gaseous mixtures of a reducing agent providing hydrogen isotopes and interhalogen compounds are uniformly ignited by means of an electrical discharge, flash- photolysis or an electron beam. The resulting chemical explosion pumps a lasing chemical species, hydrogen fluoride or deuterium fluoride which is formed in the chemical reaction. The generated lasing pulse has light frequencies in the 3- micron range. Suitable interhalogen compounds include bromine trifluoride (BrF$sub 3$), bromine pentafluoride (BrF$sub 5$), chlorine monofluoride (ClF), chlorine trifluoride (ClF$sub 3$), chlorine pentafluoride (ClF$sub 5$), iodine pentafluoride (IF$sub 5$), and iodine heptafluoride (IF$sub 7$); and suitable reducing agents include hydrogen (H$sub 2$), hydrocarbons such as methane (CH$sub 4$), deuterium (D$sub 2$), and diborane (B$sub 2$H$sub 6$), as well as combinations of the gaseous compound and/or molecular mixtures of the reducing agent.

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

Bie Haiying; Lu Jing; Yu Jiehui

Three novel thiocyanate supramolecular compounds have been synthesized and characterized by X-ray diffraction and fluorescent spectra. Compound [pipH]{sub 2}[Co(NCS){sub 4}] (pip=piperazine) 1 possesses a two-dimensional layer connected by the combination of N-H...N hydrogen bonds and weak S...S contacts. Under the same conditions, using nickel salt instead of cobalt salt as a starting material, we obtained a different two-dimensional supramolecular layer [pipH]{sub 2}[Ni(NCS){sub 4}] 2 connected by unusual N-H...S hydrogen bonds and weak S...S contacts. In order to observe the influence of the dimension of ligand on the self-assembly structure, dabco was used for substituting pip, and compound [dabcoH]{sub 2}[Ni(NCS){sub 4}]more » (dabco=1,4-Diazabicyclo[2.2.2] octane) 3 was gained, which constructed two-dimensional, highly wavy network with hourglass-shaped cavities only through N-H...S hydrogen bonds.« less

The study of interaction between PFOA/PFOS and uracil by topology quality and spectroscopic analysis

NASA Astrophysics Data System (ADS)

Xu, Hui-Ying; Zhu, Jian-Qing; Wang, Wei; Xu, Xiao-Lu; Lu, Yin

2014-02-01

It has been established that perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS) can be considered as emerging persistent organic pollutants. In recent years, there was increasing distribution of PFOA/PFOS in environmental systems, and accumulation and toxic effects of PFOA/PFOS in human body. In this paper, quantum chemistry methods were employed to study the interaction between perfluorinated organic pollutants and base (uracil). The results showed that there were four stable binding modes between the two perfluorinated compounds with uracil, especially the second mode which caused the most detrimental physiological functional response. NBO analysis showed that reactive hydrogen in the two perfluorinated compounds had the greatest effect on the hydrogen bond. The nature of the hydrogen bond formed between the two perfluorinated compounds and base was investigated using the AIM theory. The changes of spectroscopic properties in complexes were analyzed by IR and NMR spectra.

Structure-Activity Studies of Semiochemicals from the Spider Orchid Caladenia plicata for Sexual Deception.

PubMed

Bohman, Bjorn; Karton, Amir; Flematti, Gavin R; Scaffidi, Adrian; Peakall, Rod

2018-05-01

Sexually deceptive orchids attract specific pollinators by mimicking insect sex pheromones. Normally this mimicry is very specific and identical compounds have been identified from orchids and matching females of the pollinators. In this study, we conduct a detailed structure-activity investigation on isomers of the semiochemicals involved in the sexual attraction of the male pollinator of the spider orchid Caladenia plicata. This orchid employs an unusual blend of two biosynthetically unrelated compounds, (S)-β-citronellol and 2-hydroxy-6-methylacetophenone, to lure its Zeleboria sp. thynnine wasp pollinator. We show that the blend is barely attractive when (S)-β-citronellol is substituted with its enantiomer, (R)-β-citronellol. Furthermore, none of the nine-possible alternative hydroxy-methylacetophenone regioisomers of the natural semiochemical are active when substituted for the natural 2-hydroxy-6-methylacetophenone. Our results were surprising given the structural similarity between the active compound and some of the analogues tested, and results from previous studies in other sexually deceptive orchid/wasp systems where substitution with analogues was possible. Interestingly, high-level ab initio and density functional theory calculations of the hydroxy-methylacetophenones revealed that the active natural isomer, 2-hydroxy-6-methylacetophenone, has the strongest intramolecular hydrogen bond of all regioisomers, which at least in part may explain the specific activity.

HEAVY METAL LOADED PLASTIC SCINTILLATING COMPOSITIONS

DOEpatents

Hyman, M. Jr.

1962-06-26

Thls lnventlon relates to a plastlc sclntlllatlon composltlon havlng lncorporated ln the base plastlc a lead compound. Thls compound forms a haze- free sclntillator. The lead compound has the general formula (R/sub 4/) x from the group consisting of hydrogen, alky, and phenyl, R4 ls selected from the group conslstlng of acrylyl and methacryiyl radlcals, and x ls a number from 0,5 to 1; however, when R/sub 1/, R/sub 2/, and R/sub 3/ are all hydrogen the x ls equal to 1. The phosphor ln the sclntlllatlng compositlon and the lead compound can be dlssolved ln a polymerlc resln selected from the group conslsting of polyvinyl toluene and copolymers of vlnyl toluene and cyclohexyl methacrylate. (AEC)

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

Schrock, Richard Royce; Autenrieth, Benjamin

The present invention, among other things, provides highly syndiotactic poly(dicyclopentadiene) and/or hydrogenated poly(dicyclopentadiene), compositions thereof, and compounds and methods for preparing the same. In some embodiments, a provided compound is a compound of formula I, II or III. In some embodiments, a provided method comprises providing a compound of formula I, II or III.

Hydrogen bonds directed 2D → 3D interdigitated Cd(II) compound: Synthesis, crystal structure and dual-emission luminescent properties

NASA Astrophysics Data System (ADS)

Yu, Yuanyuan

2017-06-01

A new Cd(II) compound, namely [Cd2(btc)(phen)2Cl]n·n(H2O)·n(DMA) (1, H3btc = 1, 3, 5-benzenetricarboxylic acid, phen = 1,10-phenanthroline, DMA = N,N'-dimethylacetamide) has been synthesized and structurally characterized by single-crystal X-ray diffraction analysis. This compound crystallizes in monoclinic P21/n space group with a = 13.5729(7) Å, b = 20.1049(7) Å, c = 13.9450(6) Å, β = 104.671(4)°, Z = 4. Single-crystal X-ray diffraction analysis reveals that compound 1 features a 2D → 3D interdigitated framework directed by the intermolecular hydrogen bonds. In addition, the luminescent properties of compound 1 were also investigated in the solid state at room temperature.

Hydrogenation of carbonyl compounds of relevance to hydrogen storage in alcohols

NASA Astrophysics Data System (ADS)

Suárez, Andrés

2018-02-01

Alcohols are a promising source for the sustainable production of hydrogen that may also serve as rechargeable liquid organic hydrogen carriers (LOHCs). Metal-catalyzed acceptorless dehydrogenation of alcohols produces carbonyl derivatives as H2-depleted by-products, which by means of a hydrogenation reaction can be reconverted to the initial alcohols. Hence, reversible H2-storage systems based on pairs of secondary alcohols/ketones and primary alcohols/carboxylic acid derivatives may be envisaged. In this contribution, the hydrogenation of carbonyl derivatives, including ketones, esters, amides and carboxylic acids, is reviewed from the perspective of the hydrogen storage in alcohols.

Synthesis of C60H2 by rhodium-catalyzed hydrogenation of C60

NASA Technical Reports Server (NTRS)

Becker, L.; Evans, T. P.; Bada, J. L.; Miller, S. L. (Principal Investigator)

1993-01-01

Reduction of C60 with rhodium(0) on alumina and hydrogen in deuterated benzene (C6D6) at ambient temperature and pressure yields a mixture of hydrogenated compounds; C60H2 has been characterized as the major product in 14% yield based on 1H NMR.

Name that compound: The numbers game for CFCs, HFCs, HCFCs, and Halons

DOE Data Explorer

Blasing, T. J.; Jones, Sonja

2012-02-01

Chlorofluorocarbons (CFCs) contain Carbon and some combination of Fluorine and Chlorine atoms. Hydrofluorocarbons (HFCs) contain Hydrogen, Fluorine, and Carbon (no chlorine). Hydrochlorofluorocarbons (HCFCs) contain Hydrogen, Chlorine, Fluorine, and Carbon atoms. Hydrobromofluorocarbons (HBFCs) contain Hydrogen, Bromine, Fluorine, and Carbon atoms. Perfluorocarbons contain Fluorine, Carbon, and Bromine atoms, and some contain Chlorine and/or Hydrogen atoms. These compounds are often designated by a combination of letters and numbers (e.g., CFC-11, HCFC-142b). In the latter example, the lower-case b refers to an isomer, which has no relationship to the chemical formula (C2H3F2Cl), but designates a particular structural arrangement of the atoms included. For example, HCFC-142b identifies the isomer in which all three hydrogen atoms are attached to the same carbon atom, and the structural formula is written as CH3CF2Cl. By contrast, HCFC-142 (without the b) refers to an arrangement in which one carbon atom is attached to two hydrogen atoms and one chlorine atom, while the other carbon atom is attached to the third hydrogen atom and two fluorine atoms. Hence, it has a different structural formula (CH2ClCHF2).

Calculated Properties of Fully Hydrogenated Single Layers of BN, BC2N, and Graphene: Graphane and Its BN-Containing Analogues

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

Averill, Frank; Morris, James R; Cooper, Valentino R

2009-01-01

Carbon is an attractive material for hydrogen adsorption, due to its light weight, variety of structures, and ability to both physisorb and chemisorb hydrogen. Recently, fully hydrogenated graphene layers ( graphane ) have been predicted to exist [J.O. Sofo et al., Phys. Rev. B 75, 15340 (2007)], and experimentally observed [D.C. Elias et al., Science 323, 610 (2009)]. In this work, we examine analogues of graphane, in particular BNH2 and BC2NH4. Unlike graphene, these materials have a band gap without hydrogenation. Our results indicate that the hydrogenation product of BN is metastable: the fully hydrogenated compound BNH2 is higher inmore » energy than hexagonal BN sheets plus H2 molecules, in sharp contrast with graphane. We find that BC2NH4 is energetically very close to hexagonal BC2N+2H2 molecules. Furthermore our examination of the relative binding strengths of rows of symmetry related hydrogen atoms on BC2NH4shows that this compound is marginally higher in energy than BC2NH2 plus an H2 molecule, with the hydrogen atoms in BC2NH2 absorbed on the carbon sites. These remaining hydrogen atoms are not as strongly bound as in graphane, indicating that the average hydrogen chemisorption energy is controllable by changing the carbon content in the B-C-N layer.« less

Morphology, mechanical, cross-linking, thermal, and tribological properties of nitrile and hydrogenated nitrile rubber/multi-walled carbon nanotubes composites prepared by melt compounding: The effect of acrylonitrile content and hydrogenation

NASA Astrophysics Data System (ADS)

Likozar, Blaž; Major, Zoltan

2010-11-01

The purpose of this work was to prepare nanocomposites by mixing multi-walled carbon nanotubes (MWCNT) with nitrile and hydrogenated nitrile elastomers (NBR and HNBR). Utilization of transmission electronic microscopy (TEM), scanning electron microscopy (SEM), and small- and wide-angle X-ray scattering techniques (SAXS and WAXS) for advanced morphology observation of conducting filler-reinforced nitrile and hydrogenated nitrile rubber composites is reported. Principal results were increases in hardness (maximally 97 Shore, type A), elastic modulus (maximally 981 MPa), tensile strength (maximally 27.7 MPa), elongation at break (maximally 216%), cross-link density (maximally 7.94 × 1028 m-3), density (maximally 1.16 g cm-3), and tear strength (11.2 kN m-1), which were clearly visible at particular acrylonitrile contents both for unhydrogenated and hydrogenated polymers due to enhanced distribution of carbon nanotubes (CNT) and their aggregated particles in the applied rubber matrix. Conclusion was that multi-walled carbon nanotubes improved the performance of nitrile and hydrogenated nitrile rubber nanocomposites prepared by melt compounding.

Hydrogen production profiles using furans in microbial electrolysis cells.

PubMed

Catal, Tunc; Gover, Tansu; Yaman, Bugra; Droguetti, Jessica; Yilancioglu, Kaan

2017-06-01

Microbial electrochemical cells including microbial fuel cells (MFCs) and microbial electrolysis cells (MECs) are novel biotechnological tools that can convert organic substances in wastewater or biomass into electricity or hydrogen. Electroactive microbial biofilms used in this technology have ability to transfer electrons from organic compounds to anodes. Evaluation of biofilm formation on anode is crucial for enhancing our understanding of hydrogen generation in terms of substrate utilization by microorganisms. In this study, furfural and hydroxymethylfurfural (HMF) were analyzed for hydrogen generation using single chamber membrane-free MECs (17 mL), and anode biofilms were also examined. MECs were inoculated with mixed bacterial culture enriched using chloroethane sulphonate. Hydrogen was succesfully produced in the presence of HMF, but not furfural. MECs generated similar current densities (5.9 and 6 mA/cm 2 furfural and HMF, respectively). Biofilm samples obtained on the 24th and 40th day of cultivation using aromatic compounds were evaluated by using epi-fluorescent microscope. Our results show a correlation between biofilm density and hydrogen generation in single chamber MECs.

pH-Dependent isotope exchange and hydrogenation catalysed by water-soluble NiRu complexes as functional models for [NiFe]hydrogenases.

PubMed

Kure, Bunsho; Matsumoto, Takahiro; Ichikawa, Koji; Fukuzumi, Shunichi; Higuchi, Yoshiki; Yagi, Tatsuhiko; Ogo, Seiji

2008-09-21

The pH-dependent hydrogen isotope exchange reaction between gaseous isotopes and medium isotopes and hydrogenation of the carbonyl compounds have been investigated with water-soluble bis(mu-thiolate)(mu-hydride)NiRu complexes, Ni(II)(mu-SR)(2)(mu-H)Ru(II) {(mu-SR)(2) = N,N'-dimethyl-N,N'-bis(2-mercaptoethyl)-1,3-propanediamine}, as functional models for [NiFe]hydrogenases. In acidic media (at pH 4-6), the mu-H ligand of the Ni(II)(mu-SR)(2)(mu-H)Ru(II) complexes has H(+) properties, and the complexes catalyse the hydrogen isotope exchange reaction between gaseous isotopes and medium isotopes. A mechanism of the hydrogen isotope exchange reaction between gaseous isotopes and medium isotopes through a low-valent Ni(I)(mu-SR)(2)Ru(I) complex is proposed. In contrast, in neutral-basic media (at pH 7-10), the mu-H ligand of the Ni(II)(mu-SR)(2)(mu-H)Ru(II) complexes acts as H(-), and the complexes catalyse the hydrogenation of carbonyl compounds.

CATALYTIC PROPERTIES OF SEMICONDUCTORS.

DTIC Science & Technology

SEMICONDUCTORS, CATALYSTS), (*CATALYSIS, REACTION KINETICS), (* SODIUM COMPOUNDS, TUNGSTATES), (*GALLIUM ALLOYS, ARSENIC ALLOYS), (*YTTERBIUM...COMPOUNDS, SILICIDES ), (*GERMANIUM, CATALYSIS), INTERNAL CONVERSION, EXCHANGE REACTIONS, HEAT OF ACTIVATION, THERMODYNAMICS, DEUTERIUM, POWDERS, SURFACES, HYDROGEN

Analysis of oxidised heavy paraffininc products by high temperature comprehensive two-dimensional gas chromatography.

PubMed

Potgieter, H; Bekker, R; Beigley, J; Rohwer, E

2017-08-04

Heavy petroleum fractions are produced during crude and synthetic crude oil refining processes and they need to be upgraded to useable products to increase their market value. Usually these fractions are upgraded to fuel products by hydrocracking, hydroisomerization and hydrogenation processes. These fractions are also upgraded to other high value commercial products like lubricant oils and waxes by distillation, hydrogenation, and oxidation and/or blending. Oxidation of hydrogenated heavy paraffinic fractions produces high value products that contain a variety of oxygenates and the characterization of these heavy oxygenates is very important for the control of oxidation processes. Traditionally titrimetric procedures are used to monitor oxygenate formation, however, these titrimetric procedures are tedious and lack selectivity toward specific oxygenate classes in complex matrices. Comprehensive two-dimensional gas chromatography (GC×GC) is a way of increasing peak capacity for the comprehensive analysis of complex samples. Other groups have used HT-GC×GC to extend the carbon number range attainable by GC×GC and have optimised HT-GC×GC parameters for the separation of aromatics, nitrogen-containing compounds as well as sulphur-containing compounds in heavy petroleum fractions. HT-GC×GC column combinations for the separation of oxygenates in oxidised heavy paraffinic fractions are optimised in this study. The advantages of the HT-GC×GC method in the monitoring of the oxidation reactions of heavy paraffinic fraction samples are illustrated. Copyright © 2017 Elsevier B.V. All rights reserved.

METHOD OF REDUCING PLUTONIUM COMPOUNDS

DOEpatents

Johns, I.B.

1958-06-01

A method is described for reducing plutonium compounds in aqueous solution from a higher to a lower valence state. This reduction of valence is achieved by treating the aqueous solution of higher valence plutonium compounds with hydrogen in contact with an activated platinum catalyst.

Chemical Reactions in Supercritical Carbon Dioxide

NASA Astrophysics Data System (ADS)

Wai, Chien M.; Hunt, Fred; Ji, Min; Chen, Xiaoyuan

1998-12-01

Utilizing supercritical fluids as environmentally benign solvents for chemical synthesis is one of the new approaches in the "greening" of chemistry. Carbon dioxide is the most widely used gas for supercritical fluid studies because of its moderate critical constants, nontoxic nature, and availability in pure form. One unique property of supercritical carbon dioxide (sc-CO2) is its high solubility for fluorinated compounds. Thus sc-CO2 can be used to replace Freons that are conventionally used as solvents for synthesis of perfluoro-polymers. Another property of sc-CO2 is its miscibility with gases such as H2. Heterogeneous reactions involving these gases may become homogeneous reactions in sc-CO2. Reactions in sc-CO2 may offer several advantages including controlling phase behavior and products, increasing speed of reactions, and obtaining specific reaction channels. This paper describes the following nine types of chemical reactions reported in the literature utilizing sc-CO2 as a solvent to illustrate the unique properties of the supercritical fluid reaction systems: (i) hydrogenation and hydroformylation, (ii) synthesis of organometallic compounds, (iii) metal chelation and extraction, (iv) preparation of inorganic nanoparticles, (v) stereo-selectivity of lipase-catalyzed reactions, (vi) asymmetric catalytic hydrogenation, (vii) polymerization, (viii) Diels-Alder reaction, and (ix) free radical reactions.

Hydrogen and its compounds under extreme pressure

NASA Astrophysics Data System (ADS)

Utyuzh, A. N.; Mikheyenkov, A. V.

2017-12-01

In the last two or three years, significant advances in the study of hydrogen and its compounds under extreme conditions (ultrahigh pressures over a wide temperature range) have notably changed the hydrogen phase diagram, provided a break-through in understanding hydrides’ behavior under pressure (as exemplified by the discovery of high-temperature superconductivity in hydrogen sulfide), and, finally, enabled achieving cold metallization of hydrogen. The situation prior to the 2010s is reviewed in brief and more recent work is examined in detail. While the primary focus is on experimental research, mention is also made of the theoretical and numerical work it stimulates. This review presents an extension of the talk by the authors for the scientific session of the Physical Sciences Division of the Russian Academy of Sciences, “Old and new ideas in phase transition physics,” which was held on December 21, 2016 (see Phys. Usp. 60 948-957 (2017); Usp. Fiz. Nauk 187 1021 (2017)). (Editor’s note.)

Hydrogen atom donor compounds as contrast enhancers for black-and-white photothermographic and thermographic elements

DOEpatents

Harring, Lori S.; Simpson, Sharon M.; Sansbury, Francis H.

1997-01-01

Hydrogen atom donor compounds are useful as contrast enhancers when used in combination with (i) hindered phenol developers, and (ii) trityl hydrazide and/or formyl-phenyl hydrazine co-developers, to produce ultra-high contrast black-and-white photothermographic and thermographic elements. The photothermographic and thermographic elements may be used as a photomask in a process where there is a subsequent exposure of an ultraviolet or short wavelength visible radiation-sensitive imageable medium.

Spectroscopic studies of the intramolecular hydrogen bonding in o-hydroxy Schiff bases, derived from diaminomaleonitrile, and their deprotonation reaction products

NASA Astrophysics Data System (ADS)

Szady-Chełmieniecka, Anna; Kołodziej, Beata; Morawiak, Maja; Kamieński, Bohdan; Schilf, Wojciech

2018-01-01

The structural study of five Schiff bases derived from diaminomaleonitrile (DAMN) and 2-hydroxy carbonyl compounds was performed using 1H, 13C and 15N NMR methods in solution and in the solid state as well. ATR-FTIR and X-Ray spectroscopies were used for confirmation of the results obtained by NMR method. The imine obtained from DAMN and benzaldehyde was synthesized as a model compound which lacks intramolecular hydrogen bond. Deprotonation of all synthesized compounds was done by treating with tetramethylguanidine (TMG). NMR data revealed that salicylidene Schiff bases in DMSO solution exist as OH forms without intramolecular hydrogen bonds and independent on the substituents in aromatic ring. In the case of 2-hydroxy naphthyl derivative, the OH proton is engaged into weak intramolecular hydrogen bond. Two of imines (salDAMN and 5-BrsalDAMN) exist in DMSO solution as equilibrium mixtures of two isomers (A and B). The structures of equilibrium mixture in the solid state have been studied by NMR, ATR-FTIR and X-Ray methods. The deprotonation of three studied compounds (salDAMN, 5-BrsalDAMN, and 5-CH3salDAMN) proceeded in two different ways: deprotonation of oxygen atom (X form) or of nitrogen atom of free primary amine group of DAMN moiety (Y form). For 5-NO2salDAMN and naphDAMN only one form (X) was observed.

Control of malodorous hydrogen sulfide compounds using microbial fuel cell.

PubMed

Eaktasang, Numfon; Min, Hyeong-Sik; Kang, Christina; Kim, Han S

2013-10-01

In this study, a microbial fuel cell (MFC) was used to control malodorous hydrogen sulfide compounds generated from domestic wastewaters. The electricity production demonstrated a distinct pattern of a two-step increase during 170 h of system run: the first maximum current density was 118.6 ± 7.2 mA m⁻² followed by a rebound of current density increase, reaching the second maximum of 176.8 ± 9.4 mA m⁻². The behaviors of the redox potential and the sulfate level in the anode compartment indicated that the microbial production of hydrogen sulfide compounds was suppressed in the first stage, and the hydrogen sulfide compounds generated from the system were removed effectively as a result of their electrochemical oxidation, which contributed to the additional electricity production in the second stage. This was also directly supported by sulfur deposits formed on the anode surface, which was confirmed by analyses on those solids using a scanning electron microscope equipped with energy dispersive X-ray spectroscopy as well as an elemental analyzer. To this end, the overall reduction efficiencies for HS⁻ and H₂S(g) were as high as 67.5 and 96.4 %, respectively. The correlations among current density, redox potential, and sulfate level supported the idea that the electricity signal generated in the MFC can be utilized as a potential indicator of malodor control for the domestic wastewater system.

Multiferroic behavior associated with an order-disorder hydrogen bonding transition in metal-organic frameworks (MOFs) with the perovskite ABX3 architecture.

PubMed

Jain, Prashant; Ramachandran, Vasanth; Clark, Ronald J; Zhou, Hai Dong; Toby, Brian H; Dalal, Naresh S; Kroto, Harold W; Cheetham, Anthony K

2009-09-30

Multiferroic behavior in perovskite-related metal-organic frameworks of general formula [(CH(3))(2)NH(2)]M(HCOO)(3), where M = Mn, Fe, Co, and Ni, is reported. All four compounds exhibit paraelectric-antiferroelectric phase transition behavior in the temperature range 160-185 K (Mn: 185 K, Fe: 160 K; Co: 165 K; Ni: 180 K); this is associated with an order-disorder transition involving the hydrogen bonded dimethylammonium cations. On further cooling, the compounds become canted weak ferromagnets below 40 K. This research opens up a new class of multiferroics in which the electrical ordering is achieved by means of hydrogen bonding.

Stable hydrogen and carbon isotope ratios of extractable hydrocarbons in the Murchison meteorite

NASA Technical Reports Server (NTRS)

Krishnamurthy, R. V.; Epstein, S.; Pizzarello, S.; Cronin, J. R.; Yuen, G. U.

1991-01-01

A fairly fool-proof method to ensure that the compounds isolated from meteorites are truly part of the meteorites and not an artifact introduced by exposure to the terrestrial environment, storage, or handling is presented. The stable carbon and hydrogen isotope ratios in several of the chemical compounds extracted from the Murchison meteorite were measured. The results obtained by studying the amino acids in this meteorite gave very unusual hydrogen and carbon isotope ratios. The technique was extended to the different classes of hydrocarbons and the hydrocarbons were isolated using a variety of separation techniques. The results and methods used in this investigation are described in this two page paper.

Diverse Cd(II) compounds based on N-benzoyl-L-glutamic acid and N-donor ligands: Structures and photoluminescent properties

NASA Astrophysics Data System (ADS)

Ma, Ning; Guo, Wei-Ying; Song, Hui-Hua; Yu, Hai-Tao

2016-01-01

Five new Cd(II) coordination polymers with N-benzoyl-L-glutamic acid (H2bzgluO) and different N-donor ligands, [Cd(bzgluO)(2,2‧-bipy)(H2O)]n (1), [Cd(bzgluO)(2,4‧-bipy)2(H2O)·3H2O]n (2), [Cd(bzgluO)(phen)·H2O]n (3), [Cd(bzgluO)(4,4‧-bipy)(H2O)]n (4), [Cd(bzgluO)(bpp)(H2O)·2H2O]n (5) were synthesized (2,2‧-bipy=2,2‧-bipyridine, 2,4‧-bipy=2,4‧-bipyridine, phen=1,10-phenanthroline, 4,4‧-bipy=4,4‧-bipyridine, bpp=1,3-di(4-pyridyl)propane). Compounds 1-2 exhibit a 1D single-chain structure. Compound 1 generates a 2D supramolecular structure via π-π stacking and hydrogen bonding, 3D architecture of compound 2 is formed by hydrogen bonding. Compound 3 features a 1D double-chain structure, which are linked by π-π interactions into a 2D supramolecular layer. Compounds 4-5 display a 2D network structure. Neighboring layers of 4 are extended into a 3D supramolecular architecture through hydrogen bonding. The structural diversity of these compounds is attributed to the effect of ancillary N-donor ligands and coordination modes of H2bzgluO. Luminescent properties of 1-5 were studied at room temperature. Circular dichroism of compounds 1, 2 and 5 were investigated.

Ambient Air Monitoring for Sulfur Compounds

ERIC Educational Resources Information Center

Forrest, Joseph; Newman, Leonard

1973-01-01

A literature review of analytical techniques available for the study of compounds at low concentrations points up some of the areas where further research is needed. Compounds reviewed are sulfur dioxide, sulfuric acid, ammonium sulfate and bisulfate, metal sulfates, hydrogen sulfide, and organic sulfides. (BL)

Useful Ingredients Recovery from Sewage Sludge by using Hydrothermal Reaction

NASA Astrophysics Data System (ADS)

Suzuki, Koichi; Moriyama, Mika; Yamasaki, Yuki; Takahashi, Yui; Inoue, Chihiro

2006-05-01

Hydrothermal treatment of sludge from a sewage treatment plant was conducted to obtain useful ingredients for culture of specific microbes which can reduce polysulfide ion into sulfide ion and/or hydrogen sulfide. Several additives such as acid, base, and oxidizer were added to the hydrothermal reaction of excess sludge to promote the production of useful materials. After hydrothermal treatment, reaction solution and precipitation were qualitatively and quantitatively analyzed and estimated the availability as nutrition in cultural medium. From the results of product analysis, most of organic solid in sewage was basically decomposed by hydrothermal hydrolysis and transformed into oily or water-soluble compounds. Bacterial culture of sulfate-reducing bacteria (SRB) showed the good results in multiplication with medium which was obtained from hydrothermal treatment of sewage sludge with magnesium or calcium hydroxide and hydrogen peroxide.

Catalytic transfer hydrogenation for stabilization of bio-oil oxygenates: reduction of p-cresol and furfural over bimetallic Ni-Cu catalysts using isopropanol

USDA-ARS?s Scientific Manuscript database

Transfer hydrogenation and hydrodeoxygenation of model bio-oil compounds (p-cresol and furfural) and bio-oils derived from biomass via traditional pyrolysis and tail-gas reactive pyrolysis (TGRP) were conducted. Mild batch reaction conditions were employed, using isopropanol as a hydrogen donor over...

The effects of platinum on nickel electrodes in the nickel hydrogen cell

NASA Technical Reports Server (NTRS)

Zimmerman, Albert H.

1991-01-01

Interactions of platinum and platinum compounds with the nickel electrode that are possible in the nickel hydrogen cell, where both the nickel electrode and a platinum catalyst hydrogen electrode are in intimate contact with the alkaline electrolyte, are examined. Additionally, a mechanism of nickel cobalt oxyhydroxide formation in NiH2 cells is presented.

Survey of Chemical Compounds Tested In Vitro against Rumen Protozoa for Possible Control of Bloat

PubMed Central

Willard, F. L.; Kodras, Rudolph

1967-01-01

Over 170 chemical agents were screened for antiprotozoal action in bovine ruminal fluid. Compounds were tested at 0.1 and 0.05% concentrations. Tested compounds included inorganic compounds, antibiotics, biocides, neuromuscular agents, arsenicals, plant and animal hormones, antimalarials, surface-active agents, anthelmintics, and many others. The most active compounds were cupric sulfate, nickel sulfate, nitrofurazone, hydrogen peroxide, dodecyl sodium sulfate, pelargonic acid, iodoacetic acid, 1-diethylaminoethylamino-4-methylthiaxanthrone, sodium arsanilate, sodium arsenate, bismuth glycolyl arsanilate, 1-β-hydroxyethyl-2-methyl-5-nitroimidazole, and p-nitroaniline. Copper ion was not particularly effective against entodinia; nickel ion had no effect on holotrichs. Hydrogen peroxide and iodoacetic acid were effective at a concentration of 0.005%. Anionic surface-active agents were very effective, especially long-chain sulfates and phosphates. These antiprotozoal agents warrant further in vivo studies for possible use in treating or curing bloat in ruminants. PMID:6077407

Survey of chemical compounds tested in vitro against rumen protozoa for possible control of bloat.

PubMed

Willard, F L; Kodras, R

1967-09-01

Over 170 chemical agents were screened for antiprotozoal action in bovine ruminal fluid. Compounds were tested at 0.1 and 0.05% concentrations. Tested compounds included inorganic compounds, antibiotics, biocides, neuromuscular agents, arsenicals, plant and animal hormones, antimalarials, surface-active agents, anthelmintics, and many others. The most active compounds were cupric sulfate, nickel sulfate, nitrofurazone, hydrogen peroxide, dodecyl sodium sulfate, pelargonic acid, iodoacetic acid, 1-diethylaminoethylamino-4-methylthiaxanthrone, sodium arsanilate, sodium arsenate, bismuth glycolyl arsanilate, 1-beta-hydroxyethyl-2-methyl-5-nitroimidazole, and p-nitroaniline. Copper ion was not particularly effective against entodinia; nickel ion had no effect on holotrichs. Hydrogen peroxide and iodoacetic acid were effective at a concentration of 0.005%. Anionic surface-active agents were very effective, especially long-chain sulfates and phosphates. These antiprotozoal agents warrant further in vivo studies for possible use in treating or curing bloat in ruminants.

Bond cleavage of lignin model compounds into aromatic monomers using supported metal catalysts in supercritical water

PubMed Central

Yamaguchi, Aritomo; Mimura, Naoki; Shirai, Masayuki; Sato, Osamu

2017-01-01

More efficient use of lignin carbon is necessary for carbon-efficient utilization of lignocellulosic biomass. Conversion of lignin into valuable aromatic compounds requires the cleavage of C–O ether bonds and C–C bonds between lignin monomer units. The catalytic cleavage of C–O bonds is still challenging, and cleavage of C–C bonds is even more difficult. Here, we report cleavage of the aromatic C–O bonds in lignin model compounds using supported metal catalysts in supercritical water without adding hydrogen gas and without causing hydrogenation of the aromatic rings. The cleavage of the C–C bond in bibenzyl was also achieved with Rh/C as a catalyst. Use of this technique may greatly facilitate the conversion of lignin into valuable aromatic compounds. PMID:28387304

Volatile trace compounds released from municipal solid waste at the transfer stage: Evaluation of environmental impacts and odour pollution.

PubMed

Zhao, Yan; Lu, Wenjing; Wang, Hongtao

2015-12-30

Odour pollution caused by municipal solid waste is a public concern. This study quantitatively evaluated the concentration, environmental impacts, and olfaction of volatile trace compounds released from a waste transfer station. Seventy-six compounds were detected, and ethanol presented the highest releasing rate and ratio of 14.76 kg/d and 12.30 g/t of waste, respectively. Life cycle assessment showed that trichlorofluoromethane and dichlorodifluoromethane accounted for more than 99% of impact potentials to global warming and approximately 70% to human toxicity (non-carcinogenic). The major contributor for both photochemical ozone formation and ecotoxicity was ethanol. A detection threshold method was also used to evaluate odour pollution. Five compounds including methane thiol, hydrogen sulphide, ethanol, dimethyl disulphide, and dimethyl sulphide, with dilution multiples above one, were considered the critical compounds. Methane thiol showed the highest contribution to odour pollution of more than 90%, as indicated by its low threshold. Comparison of the contributions of the compounds to different environmental aspects indicated that typical pollutants varied based on specific evaluation targets and therefore should be comprehensively considered. This study provides important information and scientific methodology to elucidate the impacts of odourant compounds to the environment and odour pollution. Copyright © 2015 Elsevier B.V. All rights reserved.

The effect of MRET polymer compound on SAR values of RF phones.

PubMed

Smirnov, Igor

2008-01-01

This article is related to the proposed hypothesis and experimental data regarding the ability of defined polar polymer compound (MRET polymer) applied to RF phones to increase the dielectric permittivity of water based solutions and to reduce the SAR (Specific Absorption Rate) values inside the "phantom head" filled with the jelly simulating muscle and brain tissues. Due to the high organizational state of fractal structures of MRET polymer compounds and the phenomenon of piezoelectricity, this polymer generates specific subtle, low frequency, non-coherent electromagnetic oscillations (optimal random field) that can affect the hydrogen lattice of the molecular structure of water and subsequently modify the electrodynamic properties of water. The increase of dielectric permittivity of water finally leads to the reduction of the absorption rate of the electromagnetic field by living tissue. The reduction of SAR values is confirmed by the research conducted in June - July of 2006 at RF Exposure Laboratory in Escondido, California. This test also confirmed that the application of MRET polymer to RF phones does not significantly affect the air measurements of RF phone signals, and subsequently does not lead to any significant distortion of transmitted RF signals.

Superacid Catalyzed Coal Conversion Chemistry. 1st and 2nd Quarterly Technical Progress Reports, September 1, 1983-March 30, 1984.

DOE R&D Accomplishments Database

Olah, G. A.

1984-01-01

In our laboratories we have previously developed a mild coal conversion process. This involves the use of a superacid system consisting of HF and BF{sub 3} in presence of hydrogen and/or a hydrogen donor solvent. In order to understand the chemistry involved in the process of depolymerization of coal by the HF:BF{sub 3}:H{sub 2} system we are carrying out a systematic study of a number of coal model compounds. The model compounds selected for present study have two benzene rings connected with various bridging units such as alkylidene, ether, sulfide etc. From studies so far carried out it appears that high pyridine extractibilities achieved by treating coal at temperature below 100 degrees C results from the cleavage of bridges such as present in bibenzyl, diphenyl methane, dibenzyl ether, dibenzyl sulfide etc. On the other hand the increased cyclohexane extractibility and distillability observed at relatively higher temperatures and hydrogen pressures reflects the hydrogenation and cleavage of the aromatic backbone in coal structure similar to what is seen in the conversion of model compounds such as biphenyl, diphenyl ether, diphenyl sulfide, anthracene, etc.

Reversible Interconversion between 2,5-Dimethylpyrazine and 2,5-Dimethylpiperazine by Iridium-Catalyzed Hydrogenation/Dehydrogenation for Efficient Hydrogen Storage.

PubMed

Fujita, Ken-Ichi; Wada, Tomokatsu; Shiraishi, Takumi

2017-08-28

A new hydrogen storage system based on the hydrogenation and dehydrogenation of nitrogen heterocyclic compounds, employing a single iridium catalyst, has been developed. Efficient hydrogen storage using relatively small amounts of solvent compared with previous systems was achieved by this new system. Reversible transformations between 2,5-dimethylpyrazine and 2,5-dimethylpiperazine, accompanied by the uptake and release of three equivalents of hydrogen, could be repeated almost quantitatively at least four times without any loss of efficiency. Furthermore, hydrogen storage under solvent-free conditions was also accomplished. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Preliminary Results of a Modern Watershed Study from Lake Junín, Peru: Biomarker Assemblages in Terrestrial and Aquatic Plants and Surface Sediments

NASA Astrophysics Data System (ADS)

Woods, A.; Werne, J. P.; Rodbell, D. T.; Abbott, M. B.

2016-12-01

Lake Junín is a large, evaporatively-enriched lake in the central Peruvian Andes that is ideally situated to record variability in the South American Summer Monsoon, and sediment cores recovered by the Lake Junín Deep Drilling Project in 2015 span several glacial/interglacial cycles. Compound-specific stable hydrogen isotopes from leaf waxes offer the potential to reconstruct changes in monsoon strength and evapotranspiration for the entire sediment record, and can be compared with the carbonate-derived oxygen isotope record that is preserved only during interglacials. To characterize the modern proxy system, leaf samples were collected from terrestrial and aquatic species that are representative of the vegetation in the watershed. The compound distributions, concentrations, and D/H ratios of n-alkanes and n-alkanoic acids from plants and surface sediments were analyzed to develop site-specific calibrations of both terrestrial and aquatic isotopic signals, for application to downcore biomarker analyses.

Development of hydrogen gas getters for TRU waste

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

Kaszuba, J. P.; Mroz, E. J.; Peterson, E.

2004-01-01

Alpha radiolysis of hydrogenous waste and packaging materials generates hydrogen gas in radioactive storage containers. For this reason, the flammable gas (hydrogen) concentration in waste shipment containers (Transuranic Package Transporter-II or TP-II containers) is limited to the lower explosion limit of hydrogen in air (5 vol%). The use of hydrogen getters is being investigated to prevent the build up of hydrogen during storage and transport of the TP-II containers (up to 60 days). Preferred hydrogen getters are solid materials that scavenge hydrogen from the gas phase and chemically and irreversibly bind it in the solid state. One proven getter, 1,4-bis(phenylethynyl)benzenemore » or DEB, belongs to a class of compounds called alkynes, which are characterized by the presence of carbon-carbon triple bonds. These carbon atoms will, in the presence of suitable catalysts such as palladium, irreversibly react with hydrogen to form the corresponding saturated alkane compounds. Because DEB contains two triple bonds, one mole of DEB reacts with 4 moles of hydrogen. The standard formulation for the 'DEB getter' is a mixture of 75% DEB and 25% carbon catalyst (5% palladium on carbon). Certain chemicals such as volatile organic compounds (VOCs) are known to 'poison' and reduce the activity of the catalyst. Therefore, in addition to the standard formulation, a semi-permeable barrier that encapsulates and protects the getter and its catalyst from poisons was also developed. The uncoated and polymer coated getter formulations were subjected to tests that determined the performance of the getters with regard to capacity, operating temperature range (with hydrogen in nitrogen and in air), hydrogen concentration, poisons, aging, pressure, reversibility, and radiation effects. This testing program was designed to address the following performance requirements: (1) Minimum rate for hydrogen removal of 1.2E-5 moles hydrogen per second for 60 days; (2) Sufficient getter material within the TP-II to ensure that no more than 50% of getter material is consumed during the 60 days; and (3) Adequate hydrogen removal rate from the getter reaction in the absence of the recombination reaction of hydrogen to produce water. This conservative approach provides a measure of safety for waste shipments by ensuring that sufficient getter material is present and by not taking credit for the recombination reaction. The rationale for measuring and reporting the hydrogen removal rate at 50% getter capacity is thus derived. All of the coated getters as well as the uncoated DEB performed well above the performance requirements. Coating the DEB with polymers did not significantly enhance getter performance in the presence of poisons relative to uncoated DEB. The next phase of the project is to evaluate a scaled-up getter package for performance under waste shipping conditions anticipated in the TP-II.« less

Supramolecular packing and polymorph screening of N-isonicotinoyl arylketone hydrazones with phenol and amino modifications

NASA Astrophysics Data System (ADS)

Hean, Duane; Michael, Joseph P.; Lemmerer, Andreas

2018-04-01

Thirteen structural variants based on the (E)-N‧-(1-arylethylidene)pyridohydrazide template were prepared, investigated and screened for possible polymorphic behaviour. Four variants showed from Differential Scanning Calorimetry Scans thermal events indicative of new solid-state phases. The thirteen variants included substituents R = sbnd OH or sbnd NH2 placed at ortho, meta and para positions on the phenyl ring; and shifting the pyridyl nitrogen between positions 4-, 3- and 2-. The crystal structures of twelve of the compounds were determined to explore their supramolecular structures. The outcomes of these modifications demonstrated that the pyridyl nitrogen at the 2- position is 'locked' by forming a hydrogen bond with the amide hydrogen; while placing the pyridyl nitrogen at positions 3- and 4- offers a greater opportunity for hydrogen bonding with neighbouring molecules. Such interactions include Osbnd H⋯N, Nsbnd H⋯N, Osbnd H⋯O, Nsbnd H⋯O, Nsbnd H⋯π, π⋯π stacking, as well as other weaker interactions such as Csbnd H⋯N, Csbnd H⋯O, Csbnd H⋯N(pyridyl). When OH or NH2 donors are placed in the ortho position, an intramolecular hydrogen bond is formed between the acceptor hydrazone nitrogen and the respective donor. The meta- and para-positioned donors form an unpredictable array of supramolecular structures by forming hydrogen-bonded chains with the pyridyl nitrogen and carbonyl acceptors respectively. In addition to the intramolecular and chain hydrogen bond formation demonstrated throughout the crystal structures under investigation, larger order hydrogen-bonded rings were also observed in some of the supramolecular aggregations. The extent of the hydrogen-bonded ring formations range from two to six molecular participants depending on the specific crystal structure.

[Hydrogen production and enzyme activity of acidophilic strain X-29 at different C/N ratio].

PubMed

Li, Qiu-bo; Xing, De-feng; Ren, Nan-qi; Zhao, Li-hua; Song, Ye-ying

2006-04-01

Some fermentative bacteria can produce hydrogen by utilizing carbohydrate and other kinds of organic compounds as substrates. Hydrogen production was also determined by both the limiting of growth and related enzyme activity in energy metabolism. Carbon and nitrogen are needed for the growth and metabolism of microorganisms. In addition, the carbon/nitrogen (C/N) ratio can influence the material metabolized and the energy produced. In order to improve the hydrogen production efficiency of the bacteria, we analyzed the effect of different C/N ratios on hydrogen production and the related enzyme activities in the acidophilic strain X-29 using batch test. The results indicate that the differences in the metabolism level and enzyme activity are obvious at different C/N ratios. Although the difference in liquid fermentative products produced per unit of biomass is not obvious, hydrogen production is enhanced at a specifically determined ratio. At a C/N ratio of 14 the accumulative hydrogen yield of strain X-29 reaches the maximum, 2210.9 mL/g. At different C/N ratios, the expression of hydrogenase activity vary; the activity of hydrogenase decrease quickly after reaching a maximum along with the fermentation process, but the time of expression is short. The activity of alcohol dehydrogenase (ADH) tend to stabilize after reaching a peak along with the fermentation process, the difference in expression activity is little, and the expression period is long at different C/N ratios. At a C/N ratio of 14 hydrogenase and ADH reach the maximum 2.88 micromol x (min x mg)(-1) and 33.2 micromol x (min x mg)(-1), respectively. It is shown that the C/N ratio has an important effect on enhancing hydrogen production and enzyme activity.

Catalytic coal hydroliquefaction process

DOEpatents

Garg, Diwakar

1984-01-01

A process is described for the liquefaction of coal in a hydrogen donor solvent in the presence of hydrogen and a co-catalyst combination of iron and a Group VI or Group VIII non-ferrous metal or compounds of the catalysts.

Protocol for Enhanced in situ Bioremediation Using Emulsified Edible Oil

DTIC Science & Technology

2006-05-01

of molecular hydrogen include natural organic matter, fuel hydrocarbons, landfill leachate , or added organic substrates. Hydrogen is generated by... Phytoremediation of Chlorinated and Recalcitrant Compounds, p. 47-53. APPENDIX A SUBSTRATE CALCULATIONS Excel spreadsheets are

Bridged transition-metal complexes and uses thereof for hydrogen separation, storage and hydrogenation

DOEpatents

Lilga, Michael A.; Hallen, Richard T.

1990-01-01

The present invention constitutes a class of organometallic complexes which reversibly react with hydrogen to form dihydrides and processes by which these compounds can be utilized. The class includes bimetallic complexes in which two cyclopentadienyl rings are bridged together and also separately .pi.-bonded to two transition metal atoms. The transition metals are believed to bond with the hydrogen in forming the dihydride. Transition metals such as Fe, Mn or Co may be employed in the complexes although Cr constitutes the preferred metal. A multiple number of ancilliary ligands such as CO are bonded to the metal atoms in the complexes. Alkyl groups and the like may be substituted on the cyclopentadienyl rings. These organometallic compounds may be used in absorption/desorption systems and in facilitated transport membrane systems for storing and separating out H.sub.2 from mixed gas streams such as the produce gas from coal gasification processes.

Bridged transition-metal complexes and uses thereof for hydrogen separation, storage and hydrogenation

DOEpatents

Lilga, M.A.; Hallen, R.T.

1991-10-15

The present invention constitutes a class of organometallic complexes which reversibly react with hydrogen to form dihydrides and processes by which these compounds can be utilized. The class includes bimetallic complexes in which two cyclopentadienyl rings are bridged together and also separately [pi]-bonded to two transition metal atoms. The transition metals are believed to bond with the hydrogen in forming the dihydride. Transition metals such as Fe, Mn or Co may be employed in the complexes although Cr constitutes the preferred metal. A multiple number of ancillary ligands such as CO are bonded to the metal atoms in the complexes. Alkyl groups and the like may be substituted on the cyclopentadienyl rings. These organometallic compounds may be used in absorption/desorption systems and in facilitated transport membrane systems for storing and separating out H[sub 2] from mixed gas streams such as the product gas from coal gasification processes. 3 figures.

Bridged transition-metal complexes and uses thereof for hydrogen separation, storage and hydrogenation

DOEpatents

Lilga, M.A.; Hallen, R.T.

1990-08-28

The present invention constitutes a class of organometallic complexes which reversibly react with hydrogen to form dihydrides and processes by which these compounds can be utilized. The class includes bimetallic complexes in which two cyclopentadienyl rings are bridged together and also separately [pi]-bonded to two transition metal atoms. The transition metals are believed to bond with the hydrogen in forming the dihydride. Transition metals such as Fe, Mn or Co may be employed in the complexes although Cr constitutes the preferred metal. A multiple number of ancillary ligands such as CO are bonded to the metal atoms in the complexes. Alkyl groups and the like may be substituted on the cyclopentadienyl rings. These organometallic compounds may be used in absorption/desorption systems and in facilitated transport membrane systems for storing and separating out H[sub 2] from mixed gas streams such as the producer gas from coal gasification processes. 3 figs.

Bridged transition-metal complexes and uses thereof for hydrogen separation, storage and hydrogenation

DOEpatents

Lilga, Michael A.; Hallen, Richard T.

1991-01-01

The present invention constitutes a class of organometallic complexes which reversibly react with hydrogen to form dihydrides and processes by which these compounds can be utilized. The class includes bimetallic complexes in which two cyclopentadienyl rings are bridged together and also separately .pi.-bonded to two transition metal atoms. The transition metals are believed to bond with the hydrogen in forming the dihydride. Transition metals such as Fe, Mn or Co may be employed in the complexes although Cr constitutes the preferred metal. A multiple number of ancilliary ligands such as CO are bonded to the metal atoms in the complexes. Alkyl groups and the like may be substituted on the cyclopentadienyl rings. These organometallic compounds may be used in absorption/desorption systems and in facilitated transport membrane systems for storing and separating out H.sub.2 from mixed gas streams such as the product gas from coal gasification processes.

Magnetic properties and crystal structure of RENiA1 and UniA1 hydrides.

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

Bordallo, H. N.; Drulis, H.; Havela, L.

1999-08-11

RENiAl (RE = rare-earth metal) and UNiAl compounds crystallizing in the hexagonal ZrNiAl-type structure (space group P{bar 6}2m) can absorb up to 2 and 3 hydrogen (deuterium) atoms per formula unit, respectively. Hydrogenation leads to a notable lattice expansion and modification of magnetic properties. However, the impact of hydrogenation on magnetism is the opposite for 4f- and 5f-materials: TN(T{sub c})is lowered in the case of rare-earth hydrides, while for UNiAlH(D){sub x} it increases by an order of magnitude. Here we present results of magnetic and structure studies performed of these compounds, focusing on the correlation between magnetic and structural variationsmore » and discussing possible reasons of the striking difference in effect of hydrogenation on rare-earth and actinide intermetallics.« less

Self-assembling of dihydroxypropyl 5,6-dihydrothymine derivatives

NASA Astrophysics Data System (ADS)

Cetina, Mario; Makarević, Janja; Nura-Lama, Afërdita

2010-09-01

( R, S)-1-(2',3'-Dibenzoyloxypropyl)-5,6-dihydrothymine ( 2) was synthesized from ( R, S)-1-(2',3'-dihydroxypropyl)-5,6-dihydrothymine and its structure has been analyzed by X-ray diffraction, NMR and FTIR spectroscopic methods. The molecular structure and supramolecular assembling of 2 is compared with the structure of its dimesyloxypropyl analogue ( 1). Compound 1 crystallizes as cocrystal of two diastereoisomers, while 2 crystallizes as a racemic mixture. Main hydrogen-bonded motif in both compounds is dimer formed by pair of N sbnd H···O( dbnd C) hydrogen bonds, which are further linked by C sbnd H···O hydrogen bonds. Phenyl rings of dibenzoyl-dihydropyrimidine moieties of 2 participate also in supramolecular aggregation via three C sbnd H···π interactions. Hydrogen bonding as driving force of 2 self-assembly was proving by the NMR and FTIR spectroscopy.

Hydrogenated 5-carbon compound and method of making

DOEpatents

Elliott, Douglas C.; Frye, John G.

1999-01-01

The present invention is based upon the surprising discovery that a 5-carbon compound selected from the group of 4-oxopentanoic acid, at least one lactone of 4-oxopentanoic acid, and combinations thereof, may be hydrogenated with a bimetallic catalyst of a noble metal in combination with a second metal and preserve the pendant methyl group. It was further unexpectedly discovered that the same conditions of bimetallic catalyst in the presence of hydrogen are useful for catalyzing the different intermediate reactions for example angelicalactone to gamma-valerolactone and gamma-valerolactone to 1,4-pentanediol. Finally, it was surprising that levulinic acid could be converted to 2-methyltetrahydrofuran with heating in the presence of the bimetallic catalyst and hydrogen in a single process vessel. The method of the present invention unexpectedly produced a fuel or fuel component having 2-methyltetrahydrofuran either in a yield greater than 4.5 mol % or in combination with alcohols.

Hydrogenated 5-carbon compound and method of making

DOEpatents

Elliott, D.C.; Frye, J.G.

1999-03-16

The present invention is based upon the surprising discovery that a 5-carbon compound selected from the group of 4-oxopentanoic acid, at least one lactone of 4-oxopentanoic acid, and combinations thereof, may be hydrogenated with a bimetallic catalyst of a noble metal in combination with a second metal and preserve the pendant methyl group. It was further unexpectedly discovered that the same conditions of bimetallic catalyst in the presence of hydrogen are useful for catalyzing the different intermediate reactions, for example, angelicalactone to gamma-valerolactone and gamma-valerolactone to 1,4-pentanediol. Finally, it was surprising that levulinic acid could be converted to 2-methyltetrahydrofuran with heating in the presence of the bimetallic catalyst and hydrogen in a single process vessel. The method of the present invention unexpectedly produced a fuel or fuel component having 2-methyltetrahydrofuran either in a yield greater than 4.5 mol % or in combination with alcohols. 8 figs.

Mechanistic Insights and Computational Design of Transition-Metal Catalysts for Hydrogenation and Dehydrogenation Reactions.

PubMed

Chen, Xiangyang; Yang, Xinzheng

2016-10-01

Catalytic hydrogenation and dehydrogenation reactions are fundamentally important in chemical synthesis and industrial processes, as well as potential applications in the storage and conversion of renewable energy. Modern computational quantum chemistry has already become a powerful tool in understanding the structures and properties of compounds and elucidating mechanistic insights of chemical reactions, and therefore, holds great promise in the design of new catalysts. Herein, we review our computational studies on the catalytic hydrogenation of carbon dioxide and small organic carbonyl compounds, and on the dehydrogenation of amine-borane and alcohols with an emphasis on elucidating reaction mechanisms and predicting new catalytic reactions, and in return provide some general ideas for the design of high-efficiency, low-cost transition-metal complexes for hydrogenation and dehydrogenation reactions. © 2016 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Rapid Catalyst Capture Enables Metal-Free para-Hydrogen-Based Hyperpolarized Contrast Agents.

PubMed

Barskiy, Danila A; Ke, Lucia A; Li, Xingyang; Stevenson, Vincent; Widarman, Nevin; Zhang, Hao; Truxal, Ashley; Pines, Alexander

2018-05-10

Hyperpolarization techniques based on the use of para-hydrogen provide orders of magnitude signal enhancement for magnetic resonance spectroscopy and imaging. The main drawback limiting widespread applicability of para-hydrogen-based techniques in biomedicine is the presence of organometallic compounds (the polarization transfer catalysts) in solution with hyperpolarized contrast agents. These catalysts are typically complexes of platinum-group metals, and their administration in vivo should be avoided. Herein, we show how extraction of a hyperpolarized compound from an organic phase to an aqueous phase combined with a rapid (less than 10 s) Ir-based catalyst capture by metal scavenging agents can produce pure para-hydrogen-based hyperpolarized contrast agents, as demonstrated by high-resolution nuclear magnetic resonance (NMR) spectroscopy and inductively coupled plasma atomic emission spectroscopy (ICP-AES). The presented methodology enables fast and efficient means of producing pure hyperpolarized aqueous solutions for biomedical and other uses.

Methods and apparatuses for deoxygenating pyrolysis oil

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

Baird, Lance Awender; Brandvold, Timothy A.; Frey, Stanley Joseph

Methods and apparatuses are provided for deoxygenating pyrolysis oil. A method includes contacting a pyrolysis oil with a deoxygenation catalyst in a first reactor at deoxygenation conditions to produce a first reactor effluent. The first reactor effluent has a first oxygen concentration and a first hydrogen concentration, based on hydrocarbons in the first reactor effluent, and the first reactor effluent includes an aromatic compound. The first reactor effluent is contacted with a dehydrogenation catalyst in a second reactor at conditions that deoxygenate the first reactor effluent while preserving the aromatic compound to produce a second reactor effluent. The second reactormore » effluent has a second oxygen concentration lower than the first oxygen concentration and a second hydrogen concentration that is equal to or lower than the first hydrogen concentration, where the second oxygen concentration and the second hydrogen concentration are based on the hydrocarbons in the second reactor effluent.« less

A dynamic system for the simulation of fasting luminal pH-gradients using hydrogen carbonate buffers for dissolution testing of ionisable compounds.

PubMed

Garbacz, Grzegorz; Kołodziej, Bartosz; Koziolek, Mirko; Weitschies, Werner; Klein, Sandra

2014-01-23

The hydrogen carbonate buffer is considered as the most biorelevant buffer system for the simulation of intestinal conditions and covers the physiological pH range of the luminal fluids from pH 5.5 to about pH 8.4. The pH value of a hydrogen carbonate buffer is the result of a complex and dynamic interplay of the concentration of hydrogen carbonate ions, carbonic acid, the concentration of dissolved and solvated carbon dioxide and its partial pressure above the solution. The complex equilibrium between the different ions results in a thermodynamic instability of hydrogen carbonate solutions. In order to use hydrogen carbonate buffers with pH gradients in the physiological range and with the dynamics observed in vivo without changing the ionic strength of the solution, we developed a device (pHysio-grad®) that provides both acidification of the dissolution medium by microcomputer controlled carbon dioxide influx and alkalisation by degassing. This enables a continuous pH control and adjustment during dissolution of ionisable compounds. The results of the pH adjustment indicate that the system can compensate even rapid pH changes after addition of a basic or acidic moiety in amounts corresponding up to 90% of the overall buffer capacity. The results of the dissolution tests performed for a model formulation containing ionizable compounds (Nexium 20mg mups) indicate that both the simulated fasting intraluminal pH-profiles and the buffer species can significantly affect the dissolution process by changing the lag time prior to initial drug release and the release rate of the model compound. A prediction of the in vivo release behaviour of this formulation is thus most likely strongly related to the test conditions such as pH and buffer species. Copyright © 2013 Elsevier B.V. All rights reserved.

Developing clean fuels: Novel techniques for desulfurization

NASA Astrophysics Data System (ADS)

Nehlsen, James P.

The removal of sulfur compounds from petroleum is crucial to producing clean burning fuels. Sulfur compounds poison emission control catalysts and are the source of acid rain. New federal regulations require the removal of sulfur in both gasoline and diesel to very low levels, forcing existing technologies to be pushed into inefficient operating regimes. New technology is required to efficiently produce low sulfur fuels. Two processes for the removal of sulfur compounds from petroleum have been developed: the removal of alkanethiols by heterogeneous reaction with metal oxides; and oxidative desulfurization of sulfides and thiophene by reaction with sulfuric acid. Alkanethiols, common in hydrotreated gasoline, can be selectively removed and recovered from a hydrocarbon stream by heterogeneous reaction with oxides of Pb, Hg(II), and Ba. The choice of reactive metal oxides may be predicted from simple thermodynamic considerations. The reaction is found to be autocatalytic, first order in water, and zero order in thiol in the presence of excess oxide. The thiols are recovered by reactive extraction with dilute oxidizing acid. The potential for using polymer membrane hydrogenation reactors (PEMHRs) to perform hydrogenation reactions such as hydrodesulfurization is explored by hydrogenating ketones and olefins over Pt and Au group metals. The dependence of reaction rate on current density suggests that the first hydrogen addition to the olefin is the rate limiting step, rather than the adsorption of hydrogen, for all of the metals tested. PEMHRs proved unsuccessful in hydrogenating sulfur compounds to perform HDS. For the removal of sulfides, a two-phase reactor is used in which concentrated sulfuric acid oxidizes aromatic and aliphatic sulfides present in a hydrocarbon solvent, generating sulfoxides and other sulfonated species. The polar oxidized species are extracted into the acid phase, effectively desulfurizing the hydrocarbon. A reaction scheme is proposed for this system and is justified with a thermodynamic analysis and an experimental determination of the reaction rate law.

Method for the desulfurization of hot product gases from coal gasifier

DOEpatents

Grindley, Thomas

1988-01-01

The gasification of sulfur-bearing coal produces a synthesis gas which contains a considerable concentration of sulfur compounds especially hydrogen sulfide that renders the synthesis gas environmentally unacceptable unless the concentration of the sulfur compounds is significantly reduced. To provide for such a reduction in the sulfur compounds a calcium compound is added to the gasifier with the coal to provide some sulfur absorption. The synthesis gas from the gasifier contains sulfur compounds and is passed through an external bed of a regenerable solid absorbent, preferably zinc ferrite, for essentially completed desulfurizing the hot synthesis gas. This absorbent is, in turn, periodically or continuously regenerated by passing a mixture of steam and air or oxygen through the bed for converting absorbed hydrogen sulfide to sulfur dioxide. The resulting tail gas containing sulfur dioxide and steam is injected into the gasifier where the sulfur dioxide is converted by the calcium compound into a stable form of sulfur such as calcium sulfate.

Design and Characterization of Phosphine Iron Hydrides: Toward Hydrogen-Producing Catalysts.

PubMed

Weber, Katharina; Weyhermüller, Thomas; Bill, Eckhard; Erdem, Özlen F; Lubitz, Wolfgang

2015-07-20

Diamagnetic iron chloro compounds [(P(Ph)2N(Ph)2)FeCp*Cl] [1Cl] and [(P(Cy)2N(Ph)2)FeCp*Cl] [2Cl] and the corresponding hydrido complexes [(P(Ph)2N(Ph)2)FeCp*H] [1H] and [(P(Cy)2N(Ph)2)FeCp*H] [2H] have been synthesized and characterized by NMR spectroscopy, electrochemical studies, electronic absorption, and (57)Fe Mössbauer spectroscopy (P(Ph)2N(Ph)2 = 1,3,5,7-tetraphenyl-1,5-diphospha-3,7-diazacyclooctane, P(Cy)2N(Ph)2 = 1,5-dicyclohexyl-3,7-diphenyl-1,5-diphospha-3,7-diazacyclooctane, Cp* = pentamethylcyclopentadienyl). Molecular structures of [2Cl], [1H], and [2H], derived from single-crystal X-ray diffraction, revealed that these compounds have a typical piano-stool geometry. The results show that the electronic properties of the hydrido complexes are strongly influenced by the substituents at the phosphorus donor atoms of the P(R)2N(Ph)2 ligand, whereas those of the chloro complexes are less affected. These results illustrate that the hydride is a strong-field ligand, as compared to chloride, and thus leads to a significant degree of covalent character of the iron hydride bonds. This is important in the context of possible catalytic intermediates of iron hydrido species, as proposed for the catalytic cycle of [FeFe] hydrogenases and other synthetic catalysts. Both hydrido compounds [1H] and [2H] show enhanced catalytic currents in cyclic voltammetry upon addition of the strong acid trifluoromethanesulfonimide [NHTf2] (pKa(MeCN) = 1.0). In contrast to the related complex [(P(tBu)N(Bn))2FeCp(C6F5)H], which was reported by Liu et al. (Nat. Chem. 2013, 5, 228-233) to be an electrocatalyst for hydrogen splitting, the here presented hydride complexes [1H] and [2H] show the tendency for electrocatalytic hydrogen production. Hence, the catalytic direction of this class of monoiron compounds can be reversed by specific ligand modifications.

Technical and economic aspects of hydrogen storage in metal hydrides

NASA Technical Reports Server (NTRS)

Schmitt, R.

1981-01-01

The recovery of hydrogen from such metal hydrides as LiH, MgH2, TiH2, CaH2 and FeTiH compounds is studied, with the aim of evaluating the viability of the technique for the storage of hydrogen fuel. The pressure-temperature dependence of the reactions, enthalpies of formation, the kinetics of the hydrogen absorption and desorption, and the mechanical and chemical stability of the metal hydrides are taken into account in the evaluation. Economic aspects are considered. Development of portable metal hydride hydrogen storage reservoirs is also mentioned.

World Hydrogen Energy Conference, 5th, Toronto, Canada, July 15-19, 1984, Proceedings

NASA Astrophysics Data System (ADS)

Veziroglu, T. N.; Taylor, J. B.

Among the topics discussed are thermochemical and hybrid processes for hydrogen production, pyrite-assisted water electrolysis, a hydrogen distribution network for industrial use in Western Europe, the combustion of alternative fuels in spark-ignition engines, the use of fuel cells in locomotive propulsion, hydrogen storage by glass microencapsulation, and FeTi compounds' hydriding. Also covered are plasmachemical methods of energy carrier production, synthetic fuels' production in small scale plants, products found in the anodic oxidation of coal, hydrogen embrittlement, and the regulating step in LaNi5 hydride formation.

Catalysts and methods for ring opening metathesis polymerization

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

Schrock, Richard Royce; Autenrieth, Benjamin

The present invention, among other things, provides highly syndiotactic poly(dicyclopentadiene) and/or hydrogenated poly(dicyclopentadiene), compositions thereof, and compounds and methods for preparing the same. In some embodiments, a provided compound is a compound of formula I, II or III. In some embodiments, a provided method comprises providing a compound of formula I, II or III.

Combustion Products Monitor: Trade Study Testing

NASA Technical Reports Server (NTRS)

Wallace, William T.; Trowbridge, John B.

2011-01-01

Current combustion products monitoring on the International Space Station (ISS) uses a handheld device (Compound Specific Analyzer-Combustion Products, CSA-CP) containing electrochemical sensors used to measure the concentration of carbon monoxide (CO), hydrogen chloride (HCl), hydrogen cyanide (HCN), and oxygen (O2). The CO sensor in this device accounts for a well-known cross-sensitivity with hydrogen (H2), which is important, as ISS air can contain up to 100 ppm H2. Unfortunately, this current device is being discontinued, and due to space constraints, the new model cannot accommodate the size of the current CO sensor. Therefore, a trade study was conducted in order to determine which CO sensors on the market were available with compensation for H2, and which instruments used these sensors, while also measuring HCN, O2, and carbon dioxide (CO2). The addition of CO2 to the device is helpful, as current monitoring of this gas requires a second hand-held monitor. By providing a device that will monitor both combustion products and CO2, volume and up-mass can be reduced as these monitors are delivered to ISS.

Biofiltration of odors, toxics and volatile organic compounds from publicly owned treatment works

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

Webster, T.S.; Devinny, J.S.; Torres, E.M.

1996-12-31

Increasing federal and state regulation has made it necessary to apply air pollution control measures at publicly owned treatment works (POTWs). Traditional control technologies may not be suitable for treating the low and variable contaminant concentrations often found in POTW off-gases. An alternative control technology, biofiltration, was studied. An experiment using bench- and pilot-scale reactors established optimal operating conditions for a full-scale conceptual design. The waste airstream contained ppmv levels of hydrogen sulfide and ppbv levels of specific volatile organic compounds (VOCs). Granular activated carbon (GAC) and yard waste compost (YWG) were tested as possible biofilter media with and withoutmore » pH control. The 16-month field study bench reactors achieved 99% removal of hydrogen sulfide, 53 to 98% removal of aromatic hydrocarbons, 37 to 95% removal of aldehydes and ketones, and 0 to 85% removal of chlorinated compounds. The GAC and YWC pilot reactors removed more than 80% and 65% of the total VOCs at 17 second and 70 second empty bed retention times, respectively. The YWC reactors performed poorly at empty bed retention times of 30 and 45 seconds, removing less than 40% of total VOCs. Declining pH had little negative effect on contaminant removal, suggesting costly control measures may not be necessary. Biofiltration appears to be a feasible alternative to traditional control technologies in treating off-gases from POTWs. 13 refs., 3 figs., 4 tabs.« less

From nonpeptide toward noncarbon protease inhibitors: Metallacarboranes as specific and potent inhibitors of HIV protease

PubMed Central

Cígler, Petr; Kožíšek, Milan; Řezáčová, Pavlína; Brynda, Jíří; Otwinowski, Zbyszek; Pokorná, Jana; Plešek, Jaromír; Grüner, Bohumír; Dolečková-Marešová, Lucie; Máša, Martin; Sedláček, Juraj; Bodem, Jochen; Kräusslich, Hans-Georg; Král, Vladimír; Konvalinka, Jan

2005-01-01

HIV protease (PR) represents a prime target for rational drug design, and protease inhibitors (PI) are powerful antiviral drugs. Most of the current PIs are pseudopeptide compounds with limited bioavailability and stability, and their use is compromised by high costs, side effects, and development of resistant strains. In our search for novel PI structures, we have identified a group of inorganic compounds, icosahedral metallacarboranes, as candidates for a novel class of nonpeptidic PIs. Here, we report the potent, specific, and selective competitive inhibition of HIV PR by substituted metallacarboranes. The most active compound, sodium hydrogen butylimino bis-8,8-[5-(3-oxa-pentoxy)-3-cobalt bis(1,2-dicarbollide)]di-ate, exhibited a Ki value of 2.2 nM and a submicromolar EC50 in antiviral tests, showed no toxicity in tissue culture, weakly inhibited human cathepsin D and pepsin, and was inactive against trypsin, papain, and amylase. The structure of the parent cobalt bis(1,2-dicarbollide) in complex with HIV PR was determined at 2.15 Å resolution by protein crystallography and represents the first carborane-protein complex structure determined. It shows the following mode of PR inhibition: two molecules of the parent compound bind to the hydrophobic pockets in the flap-proximal region of the S3 and S3′ subsites of PR. We suggest, therefore, that these compounds block flap closure in addition to filling the corresponding binding pockets as conventional PIs. This type of binding and inhibition, chemical and biological stability, low toxicity, and the possibility to introduce various modifications make boron clusters attractive pharmacophores for potent and specific enzyme inhibition. PMID:16227435

An enantioselective approach to the preparation of chiral sulfones by Ir-catalyzed asymmetric hydrogenation.

PubMed

Peters, Byron K; Zhou, Taigang; Rujirawanich, Janjira; Cadu, Alban; Singh, Thishana; Rabten, Wangchuk; Kerdphon, Sutthichat; Andersson, Pher G

2014-11-26

Several chiral sulfonyl compounds were prepared using the iridium catalyzed asymmetric hydrogenation reaction. Vinylic, allylic and homoallylic sulfone substitutions were investigated, and high enantioselectivity is maintained regardless of the location of the olefin with respect to the sulfone. Impressive stereoselectivity was obtained for dialkyl substitutions, which typically are challenging substrates in the hydrogenation. As expected, the more bulky Z-substrates were hydrogenated slower than the corresponding E isomers, and in slightly lower enantioselectivity.

Process to upgrade coal liquids by extraction prior to hydrodenitrogenation

DOEpatents

Schneider, Abraham; Hollstein, Elmer J.; Janoski, Edward J.; Scheibel, Edward G.

1982-01-01

Oxygen compounds are removed, e.g., by extraction, from a coal liquid prior to its hydrogenation. As a result, compared to hydrogenation of such a non-treated coal liquid, the rate of nitrogen removal is increased.

Cyclic thermochemical process for producing hydrogen using cerium-titanium compounds

DOEpatents

Bamberger, Carlos E.

1980-01-01

A thermochemical cyclic process for producing hydrogen employs the reaction between ceric oxide and titanium dioxide to form cerium titanate and oxygen. The titanate is treated with an alkali metal hydroxide to give hydrogen, ceric oxide, an alkali metal titanate and water. Alkali metal titanate and water are boiled to give titanium dioxide which, along with ceric oxide, is recycled.

Cyclic thermochemical process for producing hydrogen using cerium-titanium compounds

DOEpatents

Bamberger, C.E.

A thermochemical cyclic process for producing hydrogen employs the reaction between ceric oxide and titanium dioxide to form cerium titanate and oxygen. The titanate is treated with an alkali metal hydroxide to give hydrogen, ceric oxide, an alkali metal titanate and water. Alkali metal titanate and water are boiled to give titanium dioxide which, along with ceric oxide, is recycled.

Method of removing nitrogen monoxide from a nitrogen monoxide-containing gas using a water-soluble iron ion-dithiocarbamate, xanthate or thioxanthate

DOEpatents

Liu, David K.; Chang, Shih-Ger

1989-01-01

A method of removing nitrogen monoxide from a nitrogen monoxide-containing gas, which method comprises: (a) contacting a nitrogen oxide-containing gas with an aqueous solution of water soluble organic compound-iron ion chelate of the formula: ##STR1## wherein the water-soluble organic compound is selected from compounds of the formula: ##STR2## wherein: R is selected from hydrogen or an organic moiety having at least one polar functional group; Z is selected from oxygen, sulfur, or --N--A wherein N is nitrogen and A is hydrogen or lower alkyl having from one to four carbon atoms; and M is selected from hydrogen, sodium or potassium; and n is 1 or 2, in a contacting zone for a time and at a temperature effective to reduce the nitrogen monoxide. These mixtures are useful to provide an unexpensive method of removing NO from gases, thus reducing atmospheric pollution from flue gases.

Noble gas bond and the behaviour of XeO3 under pressure.

PubMed

Hou, Chunju; Wang, Xianlong; Botana, Jorge; Miao, Maosheng

2017-10-18

Over the past few decades, the concept of hydrogen bonds, in which hydrogen is electrophilic, has been extended to halogen bonds, chalcogen bonds and pnicogen bonds. Herein, we show that such a non-covalent bonding also exists in noble gas compounds. Using first principles calculations, we illustrate the OXe-O bond in molecular crystal XeO 3 and its effect on the behavior of this compound under pressure. Our calculations show that the covalent Xe-O bond lengths were elongated with increasing pressure and correspondingly the Xe-O stretching vibration frequencies were red shifted, which is similar to the change of H-bonds under pressure. The OXe-O bond and related hopping of O between neighboring Xe sites also correspond to the structural changes in the XeO 3 compounds at about 2 GPa. Our study extends the concept of hydrogen bonding to include all p-block elements and show a new bonding type for Noble gas elements in which it acts as an electrophilic species.

The effect of intermolecular hydrogen bonding on the fluorescence of a bimetallic platinum complex.

PubMed

Zhao, Guang-Jiu; Northrop, Brian H; Han, Ke-Li; Stang, Peter J

2010-09-02

The bimetallic platinum complexes are known as unique building blocks and arewidely utilized in the coordination-driven self-assembly of functionalized supramolecular metallacycles. Hence, photophysical study of the bimetallic platinum complexes will be very helpful for the understanding on the optical properties and further applications of coordination-driven self-assembled supramolecular metallacycles. Herein, we report steady-state and time-resolved spectroscopic experiments as well as quantum chemistry calculations to investigate the significant intermolecular hydrogen bonding effects on the intramolecular charge transfer (ICT) fluorescence of a bimetallic platinum compound 4,4'-bis(trans-Pt(PEt(3))(2)OTf)benzophenone 3 in solution. We demonstrated that the fluorescent state of compound 3 can be assigned as a metal-to-ligand charge transfer (MLCT) state. Moreover, it was observed that the formation of intermolecular hydrogen bonds can effectively lengthen the fluorescence lifetime of 3 in alcoholic solvents compared with that in hexane solvent. At the same time, the electronically excited states of 3 in solution are definitely changed by intermolecular hydrogen bonding interactions. As a consequence, we propose a new fluorescence modulation mechanism by hydrogen bonding to explain different fluorescence emissions of 3 in hydrogen-bonding solvents and nonhydrogen-bonding solvents.

The role of the reactor wall in hydrothermal biomass conversions.

PubMed

Fábos, Viktória; Yuen, Alexander K L; Masters, Anthony F; Maschmeyer, Thomas

2012-11-01

The processing of renewable feedstocks to platform chemicals and, to a lesser degree, fuels is a key part of sustainable development. In particular, the combination of lignocellulosic biomass with hydrothermal upgrading (HTU), using high temperature and pressure water (HTPW), is experiencing a renaissance. One of the many steps in this complicated process is the in-situ hydrogenation of intermediate compounds. As formic acid and related low-molecular-weight oxygenates are among the species generated, it is conceivable that they act as a hydrogen source. Such hydrogenations have been suggested to be catalyzed by water, by bases like NaOH, and/or to involve "reactive/nascent hydrogen". To achieve the temperatures and pressures required for HTU, it is necessary to conduct the reactions in high-pressure vessels. Metals are typical components of their walls and/or internal fittings. Here, using cyclohexanone as a model compound for more complex biomass-derived molecules, iron in the wall of high-pressure stainless steel reactors is shown to be responsible for the hydrogenation of ketones with low-molecular-weight oxygenates acting as a hydrogen source in combination with water. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Microsolvation of Fluoromethane.

PubMed

Rosenberg, Robert E

2016-09-29

Fluorinated organic compounds are ubiquitous in the pharmaceutical and agricultural industries. To better discern the mode of action of these compounds, it is critical to understand the potential for and strength of hydrogen bonds involving fluorine. It is known that CH3F forms a hydrogen bond with H2O in the gas phase but does not dissolve in bulk water. This paper examines CH3F surrounded by one to six water molecules. For systems of similar topologies, CH3F formed hydrogen bonds of nearly the same strength as water. Although CH3F can bind to a second water cluster with only a modest loss in binding energy, it must bind to these clusters as a double hydrogen bond acceptor. This means that CH3F cannot form a low-energy cyclic 2D hydrogen bonding network with water molecules, which limits its solubility in bulk water. However, CH3F should be able to bind to the periphery of small hydrogen bonding networks. These conclusions were not appreciably altered by SMD calculations. A more complete consideration of solvation, especially entropic effects, was not undertaken. Data for geometries, population changes, and vibrational frequency shifts were also analyzed and compared to binding energies.

Development of a Dual Plasma Desorption/Ionization System for the Noncontact and Highly Sensitive Analysis of Surface Adhesive Compounds

PubMed Central

Aida, Mari; Iwai, Takahiro; Okamoto, Yuki; Kohno, Satoshi; Kakegawa, Ken; Miyahara, Hidekazu; Seto, Yasuo; Okino, Akitoshi

2017-01-01

We developed a dual plasma desorption/ionization system using two plasmas for the semi-invasive analysis of compounds on heat-sensitive substrates such as skin. The first plasma was used for the desorption of the surface compounds, whereas the second was used for the ionization of the desorbed compounds. Using the two plasmas, each process can be optimized individually. A successful analysis of phenyl salicylate and 2-isopropylpyridine was achieved using the developed system. Furthermore, we showed that it was possible to detect the mass signals derived from a sample even at a distance 50 times greater than the distance from the position at which the samples were detached. In addition, to increase the intensity of the mass signal, 0%–0.02% (v/v) of hydrogen gas was added to the base gas generated in the ionizing plasma. We found that by optimizing the gas flow rate through the addition of a small amount of hydrogen gas, it was possible to obtain the intensity of the mass signal that was 45–824 times greater than that obtained without the addition of hydrogen gas. PMID:29234573

REDUCTION OF INORGANIC COMPOUNDS WITH MOLECULAR HYDROGEN BY MICROCOCCUS LACTILYTICUS I.

PubMed Central

Woolfolk, C. A.; Whiteley, H. R.

1962-01-01

Woolfolk, C. A. (University of Washington, Seattle) and H. R. Whiteley. Reduction of inorganic compounds with molecular hydrogen by Micrococcus lactilyticus. I. Stoichiometry with compounds of arsenic, selenium, tellurium, transition and other elements. J. Bacteriol. 84:647–658. 1962.—Extracts of Micrococcus lactilyticus (Veillonella alcalescens) oxidize molecular hydrogen at the expense of certain compounds of arsenic, bismuth, selenium, tellurium, lead, thallium, vanadium, manganese, iron, copper, molybdenum, tungsten, osmium, ruthenium, gold, silver, and uranium, as well as molecular oxygen. Chemical and manometric data indicate that the following reductions are essentially quantitative: arsenate to arsenite, pentavalent and trivalent bismuth to the free element, selenite via elemental selenium to selenide, tellurate and tellurite to tellurium, lead dioxide and manganese dioxide to the divalent state, ferric to ferrous iron, osmium tetroxide to osmate ion, osmium dioxide and trivalent osmium to the metal, uranyl uranium to the tetravalent state, vanadate to the level of vanadyl, and polymolybdate ions to molybdenum blues with an average valence for molybdenum of +5. The results of a study of certain other hydrogenase-containing bacteria with respect to their ability to carry out some of the same reactions are also presented. PMID:14001842

Fundamental relation between molecular geometry and real-space topology. Combined AIM, ELI-D, and ASF analysis of hapticities and intramolecular hydrogen-hydrogen bonds in zincocene-related compounds.

PubMed

Mebs, Stefan; Chilleck, Maren Annika; Meindl, Kathrin; Hübschle, Christian Bertram

2014-06-19

Despite numerous advanced and widely distributed bonding theories such as MO, VB, NBO, AIM, and ELF/ELI-D, complex modes of bonding such as M-Cp*((R)) interactions (hapticities) in asymmetrical metallocenes or weak intramolecular interactions (e.g., hydrogen-hydrogen (H···H) bonds) still remain a challenge for these theories in terms of defining whether or not an atom-atom interaction line (a "chemical bond") should be drawn. In this work the intramolecular Zn-C(Cp*(R)) (R = Me, -(CH2)2NMe2, and -(CH2)3NMe2) and H···H connectivity of a systematic set of 12 zincocene-related compounds is analyzed in terms of AIM and ELI-D topology combined with the recently introduced aspherical stockholder fragment (ASF) surfaces. This computational analysis unravels a distinct dependency of the AIM and ELI-D topology against the molecular geometry for both types of interactions, which confirms and extends earlier findings on smaller sets of compounds. According to these results the complete real-space topology including strong, medium, and weak interactions of very large compounds such as proteins may be reliably predicted by sole inspection of accurately determined molecular geometries, which would on the one hand afford new applications (e.g., accurate estimation of numbers, types, and strengths of intra- and intermolecular interactions) and on the other hand have deep implications on the significance of the method.

Spectroscopic studies of the intramolecular hydrogen bonding in o-hydroxy Schiff bases, derived from diaminomaleonitrile, and their deprotonation reaction products.

PubMed

Szady-Chełmieniecka, Anna; Kołodziej, Beata; Morawiak, Maja; Kamieński, Bohdan; Schilf, Wojciech

2018-01-15

The structural study of five Schiff bases derived from diaminomaleonitrile (DAMN) and 2-hydroxy carbonyl compounds was performed using 1 H, 13 C and 15 N NMR methods in solution and in the solid state as well. ATR-FTIR and X-Ray spectroscopies were used for confirmation of the results obtained by NMR method. The imine obtained from DAMN and benzaldehyde was synthesized as a model compound which lacks intramolecular hydrogen bond. Deprotonation of all synthesized compounds was done by treating with tetramethylguanidine (TMG). NMR data revealed that salicylidene Schiff bases in DMSO solution exist as OH forms without intramolecular hydrogen bonds and independent on the substituents in aromatic ring. In the case of 2-hydroxy naphthyl derivative, the OH proton is engaged into weak intramolecular hydrogen bond. Two of imines (salDAMN and 5-BrsalDAMN) exist in DMSO solution as equilibrium mixtures of two isomers (A and B). The structures of equilibrium mixture in the solid state have been studied by NMR, ATR-FTIR and X-Ray methods. The deprotonation of three studied compounds (salDAMN, 5-BrsalDAMN, and 5-CH 3 salDAMN) proceeded in two different ways: deprotonation of oxygen atom (X form) or of nitrogen atom of free primary amine group of DAMN moiety (Y form). For 5-NO 2 salDAMN and naphDAMN only one form (X) was observed. Copyright © 2017 Elsevier B.V. All rights reserved.

Hydrogen Ordering in Hexagonal Intermetallic AB5 Type Compounds

NASA Astrophysics Data System (ADS)

Sikora, W.; Kuna, A.

2008-04-01

Intermetallic compounds AB5 type (A = rare-earth atoms, B = transition metal) are known to store reversibly large amounts of hydrogen and as that are discussed in this work. It was shown that the alloy cycling stability can be significantly improved by employing the so-called non-stoichiometric compounds AB5+x and that is why analysis of change of structure turned out to be interesting. A tendency for ordering of hydrogen atoms is one of the most intriguing problems for the unsaturated hydrides. The symmetry analysis method in the frame of the theory of space group and their representation gives opportunity to find all possible transformations of the parent structure. In this work symmetry analysis method was applied for AB5+x structure type (P6/mmm parent symmetry space group). There were investigated all possible ordering types and accompanying atom displacements in positions 1a, 2c, 3g (fully occupied in stoichiometric compounds AB5), in positions 2e, 6l (where atom B could appear in non-stoichiometric compounds) and also 4h, 6m, 6k, 12n, 12o, which could be partly occupied by hydrogen as a result of hydrides. An analysis was carried out of all possible structures of lower symmetry, following from P6/mmm for we k=(0, 0, 0). Also the way of getting the structure described by the P63mc space group with double cell along the z-axiswe k=(0, 0, 0.5), as it is suggested in the work of Latroche et al. is discussed by the symmetry analysis. The analysis was obtained by computer program MODY. The program calculates the so-called basis vectors of irreducible representations of a given symmetry group, which can be used for calculation of possible ordering modes.

Effects of Post-Pyrolysis Air Oxidation of Biomass Chars on Adsorption of Neutral and Ionizable Compounds.

PubMed

Xiao, Feng; Pignatello, Joseph J

2016-06-21

This study was conducted to understand the effects of thermal air oxidation of biomass chars experienced during formation or production on their adsorptive properties toward various compounds, including five neutral nonpolar and polar compounds and seven weak acids and bases (pKa = 3-5.2) selected from among industrial chemicals and the triazine and phenoxyacetic acid herbicide classes. Post-pyrolysis air oxidation (PPAO) at 400 °C of anoxically prepared wood and pecan shell chars for up to 40 min enhanced the mass-normalized adsorption at pH ∼ 7.4 of all test compounds, especially the weak acids and bases, by up to 100-fold. Both general and specific effects were identified. The general effect results from "reaming" of pores by the oxidative removal of pore wall matter and/or tarry deposits generated during the pyrolysis step. Reaming creates new surface area and enlarges nanopores, which helps relieve steric hindrance to adsorption. The specific effect results from creation of new acidic functionality that provides sites for the formation of very strong, charge-assisted hydrogen bonds (CAHB) with solutes having comparable pKa. The CAHB hypothesis was supported by competition experiments and the finding that weak acid anion adsorption increased with surface carboxyl content, despite electrostatic repulsion from the growing negative charge. The results provide insight into the effects of air oxidation on pollutant retention.

The Mechanism of Melanocytes-Specific Cytotoxicity Induced by Phenol Compounds Having a Prooxidant Effect, relating to the Appearance of Leukoderma

PubMed Central

Ito, Shinobu; Kanazawa, Hideko; Masaki, Hitoshi

2015-01-01

Specific phenol compounds including rhododendrol (RD), a skin-brightening ingredient in cosmetics, are reported to induce leukoderma, inducing a social problem, and the elucidation of mechanism of leukoderma is strongly demanded. This study investigated the relationship among the cytotoxicities of six phenol compounds on B16F10 melanoma cells and HaCaT keratinocytes and generated reactive oxygen species (ROS). As a result, the cytotoxicity of RD on B16F10 cells was higher than that on HaCaT cells, and RD significantly increased intracellular ROS and hydrogen peroxide (H2O2) levels in B16F10 cells. Furthermore, although raspberry ketone (RK), RD derivative, also increased intracellular ROS in B16F10 cells, increase in ROS was suppressed by disodium dihydrogen ethylenediaminetetraacetate dehydrate (EDTA). The amounts of increased ROS with RK in HaCaT cells without melanocyte were further increased by tyrosinase. Therefore, tyrosinase, a metalloprotein having copper, was speculated to be one of causative agents allowing phenol compounds to work as a prooxidant. Hydroxyl radical was generated by adding a mixture of tyrosinase and H2O2 to RD, and the amount of the radical was further increased by UVB, indicating that RD cytotoxicity was caused by intracellularly increased ROS, which possibly related to phenol induced prooxidants. PMID:25861631

Discovery of new MD2 inhibitor from chalcone derivatives with anti-inflammatory effects in LPS-induced acute lung injury

PubMed Central

Zhang, Yali; Wu, Jianzhang; Ying, Shilong; Chen, Gaozhi; Wu, Beibei; Xu, Tingting; Liu, Zhiguo; Liu, Xing; Huang, Lehao; Shan, Xiaoou; Dai, Yuanrong; Liang, Guang

2016-01-01

Acute lung injury (ALI) is a life-threatening acute inflammatory disease with limited options available for therapy. Myeloid differentiation protein 2, a co-receptor of TLR4, is absolutely required for TLR4 sense LPS, and represents an attractive target for treating severe inflammatory diseases. In this study, we designed and synthesized 31 chalcone derivatives that contain the moiety of (E)-4-phenylbut-3-en-2-one, which we consider the core structure of current MD2 inhibitors. We first evaluated the anti-inflammatory activities of these compounds in MPMs. For the most active compound 20, we confirmed that it is a specific MD2 inhibitor through a series of biochemical experiments and elucidated that it binds to the hydrophobic pocket of MD2 via hydrogen bonds with Arg90 and Tyr102 residues. Compound 20 also blocked the LPS-induced activation of TLR4/MD2 -downstream pro-inflammatory MAPKs/NF-κB signaling pathways. In a rat model with ALI induced by intracheal LPS instillation, administration with compound 20 exhibited significant protective effect against ALI, accompanied by the inhibition of TLR4/MD2 complex formation in lung tissues. Taken together, the results of this study suggest the specific MD2 inhibitor from chalcone derivatives we identified is a potential candidate for treating acute inflammatory diseases. PMID:27118147

REACTIONS OF FUEL NITROGEN COMPOUNDS UNDER CONDITIONS OF INERT PYROLYSIS

EPA Science Inventory

The paper describes the pyrolysis of fossil fuels and model nitrogen compounds in helium in a small quartz plow reactor, as part of a study of the chemical mechanisms involved in the conversion of fuel-nitrogen compounds to nitric oxide (NO) during combustion. Hydrogen cyanide (H...

Method for selective dehalogenation of halogenated polyaromatic compounds

DOEpatents

Farcasiu, Malvina; Petrosius, Steven C.

1994-01-01

A method for dehalogenating halogenated polyaromatic compounds is provided wherein the polyaromatic compounds are mixed with a hydrogen donor solvent and a carbon catalyst in predetermined proportions, the mixture is maintained at a predetermined pressure, and the mixture is heated to a predetermined temperature and for a predetermined time.

Developing Health-Based Pre-Planning Clearance Goals for Airport Remediation Following Chemical Terrorist Attack: Introduction and Key Assessment Considerations

PubMed Central

Watson, Annetta; Hall, Linda; Raber, Ellen; Hauschild, Veronique D.; Dolislager, Fredrick; Love, Adam H.; Hanna, M. Leslie

2011-01-01

In the event of a chemical terrorist attack on a transportation hub, post-event remediation and restoration activities necessary to attain unrestricted facility reuse and re-entry could require hours to multiple days. While restoration timeframes are dependent on numerous variables, a primary controlling factor is the level of pre-planning and decision-making completed prior to chemical terrorist release. What follows is the first of a two-part analysis identifying key considerations, critical information, and decision criteria to facilitate post-attack and post-decontamination consequence management activities. A conceptual site model and human health-based exposure guidelines are developed and reported as an aid to site-specific pre-planning in the current absence of U.S. state or Federal values designated as compound-specific remediation or re-entry concentrations, and to safely expedite facility recovery to full operational status. Chemicals of concern include chemical warfare nerve and vesicant agents and the toxic industrial compounds phosgene, hydrogen cyanide, and cyanogen chloride. This work has been performed as a national case study conducted in partnership with the Los Angeles International Airport and The Bradley International Terminal. All recommended guidelines have been selected for consistency with airport scenario release parameters of a one-time, short-duration, finite airborne release from a single source followed by compound-specific decontamination. PMID:21390292

Developing Health-Based Pre-Planning Clearance Goals for Airport Remediation Following Chemical Terrorist Attack: Introduction and Key Assessment Considerations.

PubMed

Watson, Annetta; Hall, Linda; Raber, Ellen; Hauschild, Veronique D; Dolislager, Fredrick; Love, Adam H; Hanna, M Leslie

2011-02-13

In the event of a chemical terrorist attack on a transportation hub, post-event remediation and restoration activities necessary to attain unrestricted facility reuse and re-entry could require hours to multiple days. While restoration timeframes are dependent on numerous variables, a primary controlling factor is the level of pre-planning and decision-making completed prior to chemical terrorist release. What follows is the first of a two-part analysis identifying key considerations, critical information, and decision criteria to facilitate post-attack and post-decontamination consequence management activities. A conceptual site model and human health-based exposure guidelines are developed and reported as an aid to site-specific pre-planning in the current absence of U.S. state or Federal values designated as compound-specific remediation or re-entry concentrations, and to safely expedite facility recovery to full operational status. Chemicals of concern include chemical warfare nerve and vesicant agents and the toxic industrial compounds phosgene, hydrogen cyanide, and cyanogen chloride. This work has been performed as a national case study conducted in partnership with the Los Angeles International Airport and The Bradley International Terminal. All recommended guidelines have been selected for consistency with airport scenario release parameters of a one-time, short-duration, finite airborne release from a single source followed by compound-specific decontamination.

Developing health-based pre-planning clearance goals for airport remediation following chemical terrorist attack: Introduction and key assessment considerations

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

Watson, Annetta Paule; Raber, Ellen; Dolislager, Frederick

2011-01-01

In the event of a chemical terrorist attack on a transportation hub, post-event remediation and restoration activities necessary to attain unrestricted facility re-use and re-entry could require hours to multiple days. While restoration timeframes are dependent on numerous variables, a primary controlling factor is the level of pre-planning and decision-making completed prior to chemical terrorist release. What follows is the first of a two-part analysis identifying key considerations, critical information, and decision criteria to facilitate post-attack and post-decontamination consequence management activities. A conceptual site model and human health-based exposure guidelines are developed and reported as an aid to site-specific pre-planningmore » in the current absence of U.S. state or Federal values designated as compound-specific remediation or re-entry concentrations, and to safely expedite facility recovery to full operational status. Chemicals of concern include chemical warfare nerve and vesicant agents and the toxic industrial compounds phosgene, hydrogen cyanide, and cyanogen chloride. This work has been performed as a national case study conducted in partnership with the Los Angeles International Airport and The Bradley International Terminal. All recommended guidelines have been selected for consistency with airport scenario release parameters of a one-time, short-duration, finite airborne release from a single source followed by compound-specific decontamination.« less

Wind-Eroded Silicate as a Source of Hydrogen Peroxide on Mars

NASA Astrophysics Data System (ADS)

Bak, E. N.; Merrison, J. P.; Jensen, S. K.; Nørnberg, P.; Finster, K.

2014-07-01

Laboratory simulations show that wind-eroded silicate can be a source of hydrogen peroxide. The ubiquitous, fine-grained silicate dust might thus explain the oxidizing properties of the martian soil and affect the preservation of organic compounds.

Comprehensive physicochemical studies of a new hybrid material: 2-Amino-4-methyl-3-nitropyridinium hydrogen oxalate

NASA Astrophysics Data System (ADS)

Bryndal, I.; Kucharska, E.; Wandas, M.; Lorenc, J.; Hermanowicz, K.; Mączka, M.; Lis, T.; Marchewka, M.; Hanuza, J.

2014-01-01

A new organic-organic salt, 2-amino-4-methyl-3-nitropyridinium hydrogen oxalate (AMNPO), and its deuterium analogue have been synthesized and characterized by means of FT-IR, FT-Raman, DSC and single crystal X-ray studies. The DSC measurements and temperature dependence of the IR and Raman spectra in the range 4-295 K show that it undergoes a reversible phase transition at ∼240 K. At room temperature it crystallizes in noncentrosymmetric space group P21. The unit-cell is built of the 2-amino-4-methyl-3-nitropyridinium cations and oxalate monoanions which are connected via the Nsbnd H⋯O and Osbnd H⋯O hydrogen bonds. The geometrical and hydrogen bond parameters are similar for non-deuterated (at 120 and 293 K) and deuterated compounds (at 90 K). The phase transition is probably a consequence of order-disorder transition inside of hydrogen network. The 6-311G(2d,2p) basis set with B3LYP functional have been used to discuss the structure and vibrational spectra of the studied compound.

Synthesis, structural, DFT studies, docking and antibacterial activity of a xanthene based hydrazone ligand

NASA Astrophysics Data System (ADS)

Naseem, Saira; Khalid, Muhammad; Tahir, Muhammad Nawaz; Halim, Mohammad A.; Braga, Ataualpa A. C.; Naseer, Muhammad Moazzam; Shafiq, Zahid

2017-09-01

Herein, we present the synthesis of novel xanthene-based hydrazone (1). The chemical structure of 1 was resolved using spectroscopic techniques such as NMR, FT-IR, UV-VIS and X-ray crystallographic approaches. X-ray diffraction analysis shows that the compound (1) crystallizes in triclinic crystal lattice with the Pbar1 space group and diffused to form multi-layered structure due to non-covalent interactions such as intramolecular hydrogen bonding (H.B). In addition to experimental investigation, density functional theory (DFT) calculation with M06-2X/6-31G(d,p) and B3LYP/6-31G(d,p) level of theories was performed on compound (1) to obtain optimized geometry, spectroscopic and electronic properties. DFT optimized geometry shows good agreement with the experimental XRD structure. The hyper conjugative interactions and hydrogen bonding network are responsible for the stability of compound (1) as revealed by natural bond orbital (NBO) calculation. Moreover, hydrogen bonding network in the dimer is confirmed by FT-IR and thermodynamic studies showing excellent agreement with XRD and NBO findings. TD-DFT/UV-VIS analysis provides insight that maximum excitation is found in 1 which shows good agreement with experimental UV-VIS result. The global reactivity parameters are calculated using the energies of frontier molecular orbitals also disclosed that the compound is more stable might be due to hydrogen bonding network. Experimental and molecular docking studies indicated that this compound has anti-bacterial and anti-diabetic properties. The binding affinity of this compound against the multidrug efflux pump subunit AcrB OS=Escherichia coli (strain K12) and Human Pancreatic Alpha-Amylase is -9.2 and -10.00 kcal/mol which are higher than the control drugs. Pi-Pi, Pi-anaion, amide-pi and pi-alkyl bonds play key role in drug-protein complexes.

Impact of Supramolecular Aggregation on the Crystallization Kinetics of Organic Compounds from the Supercooled Liquid State.

PubMed

Kalra, Arjun; Tishmack, Patrick; Lubach, Joseph W; Munson, Eric J; Taylor, Lynne S; Byrn, Stephen R; Li, Tonglei

2017-06-05

Despite numerous challenges in their theoretical description and practical implementation, amorphous drugs are of growing importance to the pharmaceutical industry. One such challenge is to gain molecular level understanding of the propensity of a molecule to form and remain as a glassy solid. In this study, a series of structurally similar diarylamine compounds was examined to elucidate the role of supramolecular aggregation on crystallization kinetics from supercooled liquid state. The structural similarity of the compounds makes it easier to isolate the molecular features that affect crystallization kinetics and glass forming ability of these compounds. To examine the role of hydrogen-bonded aggregation and motifs on crystallization kinetics, a combination of thermal and spectroscopic techniques was employed. Using variable temperature FTIR, Raman, and solid-state NMR spectroscopies, the presence of hydrogen bonding in the melt and glassy state was examined and correlated with observed phase transition behaviors. Spectroscopic results revealed that the formation of hydrogen-bonded aggregates involving carboxylic acid and pyridine nitrogen (acid-pyridine aggregates) between neighboring molecules in the melt state impedes crystallization, while the presence of carboxylic acid dimers (acid-acid dimers) in the melt favors crystallization. This study suggests that glass formation of small molecules is influenced by the type of intermolecular interactions present in the melt state and the kinetics associated with the molecules to assemble into a crystalline lattice. For the compounds that form acid-pyridine aggregates, the formation of energy degenerate chains, produced due to conformational flexibility of the molecules, presents a kinetic barrier to crystallization. The poor crystallization tendency of these aggregates stems from the highly directional hydrogen-bonding interactions needed to form the acid-pyridine chains. Conversely, for the compounds that form acid-acid dimers, the nondirectional van der Waals forces needed to construct a nucleus promote rapid assembly and crystallization.

Hydrogen isotopic compositions of organic compounds in plants reflect the plant's carbon metabolism

NASA Astrophysics Data System (ADS)

Cormier, M. A.; Kahmen, A.; Werner, R. A.

2015-12-01

The main factors controlling δ2H of plant organic compounds are generally assumed to be the plant's source water and the evaporative deuterium enrichment of leaf water. Hydrogen isotope analyses of plant compounds from sediments or tree rings are therefore mainly applied to assess hydrological conditions at different spatial and temporal scales. However, the biochemical hydrogen isotope fractionation occurring during biosynthesis of plant organic compounds (ɛbio) also accounts for a large part of the variability observed in the δ2H values. Nevertheless, only few studies have directly addressed the physiological basis of this variability and even fewer studies have thus explored possible applications of hydrogen isotope variability in plant organic compounds for plant physiological research. Here we show two datasets indicating that the plant's carbon metabolism can have a substantial influence on δ2H values of n-alkanes and cellulose. First, we performed a controlled experiment where we forced plants into heterotrophic and autotrophic C-metabolism by growing them under four different light treatments. Second, we assessed the δ2H values of different parasitic heterotrophic plants and their autotrophic host plants. Our two datasets show a systematic shift in ɛbio of up to 80 ‰ depending on the plant's carbon metabolism (heterotrophic or autotrophic). Differences in n-alkane and cellulose δ2H values in plants with autotrophic vs. heterotrophic metabolisms can be explained by different NADPH pools that are used by the plants to build their compounds either with assimilates that originate directly from photosynthesis or from stored carbohydrates. Our results have significant implications for the calibration and interpretation of geological records. More importantly, as the δ2H values reflect the plant's carbon metabolism involved during the tissue formation, our findings highlight the potential of δ2H values as new tool for studying plant and ecosystem carbon metabolism.

1,4-Dihydropyridine Derivatives: Dihydronicotinamide Analogues—Model Compounds Targeting Oxidative Stress

PubMed Central

Velena, Astrida; Zarkovic, Neven; Gall Troselj, Koraljka; Bisenieks, Egils; Krauze, Aivars; Poikans, Janis; Duburs, Gunars

2016-01-01

Many 1,4-dihydropyridines (DHPs) possess redox properties. In this review DHPs are surveyed as protectors against oxidative stress (OS) and related disorders, considering the DHPs as specific group of potential antioxidants with bioprotective capacities. They have several peculiarities related to antioxidant activity (AOA). Several commercially available calcium antagonist, 1,4-DHP drugs, their metabolites, and calcium agonists were shown to express AOA. Synthesis, hydrogen donor properties, AOA, and methods and approaches used to reveal biological activities of various groups of 1,4-DHPs are presented. Examples of DHPs antioxidant activities and protective effects of DHPs against OS induced damage in low density lipoproteins (LDL), mitochondria, microsomes, isolated cells, and cell cultures are highlighted. Comparison of the AOA of different DHPs and other antioxidants is also given. According to the data presented, the DHPs might be considered as bellwether among synthetic compounds targeting OS and potential pharmacological model compounds targeting oxidative stress important for medicinal chemistry. PMID:26881016

Discovery of 8-Amino-imidazo[1,5- a ]pyrazines as Reversible BTK Inhibitors for the Treatment of Rheumatoid Arthritis

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

Liu, Jian; Guiadeen, Deodial; Krikorian, Arto

Bruton’s tyrosine kinase (BTK) is a Tec family kinase with a well-defined role in the B cell receptor (BCR) pathway. It has become an attractive kinase target for selective B cell inhibition and for the treatment of B cell related diseases. We report a series of compounds based on 8-amino-imidazo[1,5-a]pyrazine that are potent reversible BTK inhibitors with excellent kinase selectivity. Selectivity is achieved through specific interactions of the ligand with the kinase hinge and driven by aminopyridine hydrogen bondings with Ser538 and Asp539, and by hydrophobic interaction of trifluoropyridine in the back pocket. These interactions are evident in the X-raymore » crystal structure of the lead compounds 1 and 3 in the complex with the BTK enzyme. Our lead compounds show desirable PK profiles and efficacy in the preclinical rat collagen induced arthritis model.« less

Solvatochromic fluorescence characteristics of cinnamoyl pyrone derivatives

NASA Astrophysics Data System (ADS)

Benosmane, Nadjib; Boutemeur, Baya; Hamdi, Safouane M.; Hamdi, Maamar; Silva, Artur S. M.

2017-12-01

The solvatochromic fluorescence behavior of cinnamoyl pyrone derivatives has been studied in several polar and non-polar solvents. The fluorescence spectra of these compounds exhibit red shift from its absorption spectra and present an excellent correlation with solvent polarity. Cinnamoyl pyrones show a significant spectral shift in fluorescence emission as a function of water composition in binary aqueous solutions mixture. This change is due to the specific intermolecular hydrogen bonding of cinnamoyl pyrones with a molecules of water, due to the deactivation of the lowest excited singlet state of these compounds. The relative quantum yields are calculated. It is found that the quantum yields of the cinnamoyl pyrones vary with the change in the solvent polarity indicating the dependency of fluorescence properties on the solvent nature. It has been observed that the addition of water and pH medium can affect the fluorescence properties of cinnamoyl pyrones in ethanol. This study exhibited that due to the solvent sensitive emission, cinnamoyl pyrone derivatives are a good compound to be used as fluorescence probes.

Challenges towards Economic Fuel Generation from Renewable Electricity: The Need for Efficient Electro-Catalysis.

PubMed

Formal, Florian Le; Bourée, Wiktor S; Prévot, Mathieu S; Sivula, Kevin

2015-01-01

Utilizing renewable sources of energy is very attractive to provide the growing population on earth in the future but demands the development of efficient storage to mitigate their intermittent nature. Chemical storage, with energy stored in the bonds of chemical compounds such as hydrogen or carbon-containing molecules, is promising as these energy vectors can be reserved and transported easily. In this review, we aim to present the advantages and drawbacks of the main water electrolysis technologies available today: alkaline and PEM electrolysis. The choice of electrode materials for utilization in very basic and very acid conditions is discussed, with specific focus on anodes for the oxygen evolution reaction, considered as the most demanding and energy consuming reaction in an electrolyzer. State-of-the-art performance of materials academically developed for two alternative technologies: electrolysis in neutral or seawater, and the direct electrochemical conversion from solar to hydrogen are also introduced.

Bactericidal Efficacy of Hydrogen Peroxide-Based Disinfectants Against Gram-Positive and Gram-Negative Bacteria on Stainless Steel Surfaces.

PubMed

Ríos-Castillo, Abel G; González-Rivas, Fabián; Rodríguez-Jerez, José J

2017-10-01

In order to develop disinfectant formulations that leverage the effectiveness of hydrogen peroxide (H 2 O 2 ), this study evaluated the bactericidal efficacy of hydrogen peroxide-based disinfectants against Gram-positive and Gram-negative bacteria on stainless steel surfaces. Low concentration of hydrogen peroxide as 0.5% with a cationic polymer, ethoxylated fatty alcohol, and ethyl alcohol had bactericidal efficacy (reductions ≥ 4 log 10 CFU/mL) against Escherichia coli, Staphylococcus aureus, Enterococcus hirae, and Pseudomonas aeruginosa. Hydrogen peroxide-based disinfectants were more effective against E. hirae and P. aeruginosa than to S. aureus. However, the efficacy of hydrogen peroxide against catalase positive bacteria such as S. aureus was increased when this compound was formulated with low concentrations of benzalkonium chloride or ethyl alcohol, lactic acid, sodium benzoate, cationic polymer, and salicylic acid. This study demonstrates that the use of hydrogen peroxide with other antimicrobial products, in adequate concentrations, had bactericidal efficacy in Gram-positive and Gram-negative bacteria on stainless steel surfaces, enabling to reduce the effective concentration of hydrogen peroxide. In the same way, the use of hydrogen peroxide-based disinfectants could reduce the concentrations of traditional disinfectants as quaternary ammonium compounds and therefore a reduction of their chemical residues in the environment after being used. The study of the bactericidal properties of environmentally nontoxic disinfectants such as hydrogen peroxide, sole or in formulations with other disinfectants against Gram-positive and Gram-negative bacteria can enhance the efficacy of various commonly used disinfectant formulations with the hygiene benefits that it entails. Also, the use of hydrogen peroxide formulations can reduce the concentration levels of products that generate environmental residues. © 2017 Institute of Food Technologists®.

Process for reproducibly preparing titanium subhydride

DOEpatents

Carlson, Richard S.

1982-01-01

Titanium subhydride is produced in a reactor by heating a selected amount of finely divided titanium compound at a selected temperature for a selected period of time under dynamic vacuum conditions. Hydrogen is removed substantially uniformly from each powder grain and there is produced a subhydride of substantially uniform titanium-hydrogen composition. Selection of the amount, temperature and time produces a subhydride of selected titanium-hydrogen composition.

3-(4-Methoxy­phen­yl)pent-2-ene-1,5-dioic acid

PubMed Central

Das, Ushati; Chheda, Shardul B.; Pednekar, Suhas R.; Karambelkar, Narendra P; Guru Row, T. N.

2008-01-01

In the title compound, C12H12O5, mol­ecules are linked into anti­parallel hydrogen-bonded sheets through inversion dimers generated via two O—H⋯O hydrogen bonds. Using the R 2 2(8) motif as a building block, hydrogen-bonded chains of a C 2 2(8) superstructure are then generated. PMID:21581357

Water Table Depth Reconstruction in Ombrotrophic Peatlands Using Biomarker Abundance Ratios and Compound-Specific Hydrogen Isotope Composition

NASA Astrophysics Data System (ADS)

Nichols, J. E.; Jackson, S. T.; Booth, R. K.; Pendall, E. G.; Huang, Y.

2005-12-01

Sediment cores from ombrotrophic peat bogs provide sensitive records of changes in precipitation/evaporation (P/E) balance. Various proxies have been developed to reconstruct surface moisture conditions in peat bogs, including testate amoebae, plant macrofossils, and peat humification. Studying species composition of testate amoeba assemblages is time consuming and requires specialized training. Humification index can be influenced by environmental factors other than moisture balance. The plant macrofossil proxy is less quantitative and cannot be performed on highly decomposed samples. We demonstrate that the ratio of C23 alkane to C29 alkane abundance may provide a simple alternative or complementary means of tracking peatland water-table depth. Data for this proxy can be collected quickly using a small sample (100 mg dry). Water-table depth decreases during drought, and abundance of Sphagnum, the dominant peat-forming genus, decreases as vascular plants increase. Sphagnum moss produces mainly medium chain-length alkanes (C21-C25) while vascular plants (grasses and shrubs) produce primarily longer chain-length alkanes (C27-C31). Therefore, C23:C29 n-alkane ratios quantitatively track the water table depth fluctuations in peat bogs. We compared C23:C29 n-alkane ratios in a core from Minden Bog (southeastern Michigan) with water table depth reconstructions based on testate-amoeba assemblages and humification. The 184-cm core spans the past ~3kyr of continuous peat deposition in the bog. Our results indicate that the alkane ratios closely track the water table depth variations, with C29 most abundant during droughts. We also explored the use of D/H ratios in Sphagnum biomarkers as a water-table depth proxy. Compound-specific hydrogen isotope ratio analyses were performed on Sphagnum biomarkers: C23 and C25 alkane and C24 acid. Dry periods are represented in these records by an enrichment of deuterium in these Sphagnum-specific compounds. These events also correlate with drought events in the testate amoeba record and the alkane abundance ratio record. These biogeochemical proxies can be used in paleohydrological studies of ombrotrophic bogs and provide a new and complimentary source of data from these underutilized paleoclimate archives.

Perfluoroalkyl acids: recent research highlights

EPA Science Inventory

Perfluorinated compounds are organic chemicals in which all hydrogen molecules of the carbon-chain are substituted by fluorine molecules. Generally, there are two types of perfluorinated compounds, the perfluoroalkanes that are primarily used clinically for oxygenation and respir...

The Addition of Several Mineral Sources on Growing Media of Fluorescent Pseudomonad for the Biosynthesis of Hydrogen Cyanide

NASA Astrophysics Data System (ADS)

Advinda, L.; Fifendy, M.; Anhar, A.

2018-04-01

All Fluorescent pseudomonad is a group of rhyzobacteria which these days often utilized on plant disease control. The growing media is an absolute requirement which needs to be considered for the growth and cultivation of bacteria. The mineral source contained in growing media of bacteria may affect the production of hydrogen cyanide compound. The objectives of the research were to obtain the best source of minerals for biosynthesis of cyanide acid compounds by fluorescent pseudomonad isolates PfPj1, PfPb1, PfPj2, Kd7, Cas, Cas3, and LAHp2. This research is a qualitative experimental research including observation of hydrogen cyanide compound produced after the growing media of fluorescent pseudomonad bacteria added with several mineral sources. The treatments were given: A = ZnSO4.7H2O 0.5 mM addition, B = CoCl2.6H2O 0.5 mM addition, and C = Fe2SO4.7H2O 0.5 mM addition. From the result of the research, it was concluded that the addition of ZnSO4.7H2O mineral resources on the growing media of fluorescent pseudomonad isolate Cas and Cas3 produced the best hydrogen cyanide. Whereas addition of CoCl2.6H2O mineral source on the growing media showed poor hydrogen cyanide production for all fluorescent pseudomonad isolates

Symmetry analysis of the behavior of the family R6M23 compounds upon hydrogenation

NASA Astrophysics Data System (ADS)

Kuna, Agnieszka; Sikora, Wiesława

2011-06-01

Symmetry analysis was applied in this work to discuss the behavior of the family R6M23 compounds upon hydrogenation (deuteration), where different structural transformations and magnetic properties, depending on the type of R and M atoms and hydrogen (deuterium) concentrations, have been found. The crystallographic structure of these compounds is described by the Fm3m space group and contain 116 atoms per unit cell occupying the positions 24e(R), 4b, 24d, 32f1 and 32f2(M). Additionally in the elementary cell, there could be up to 100 atoms of hydrogen (or deuterium) occupying the interstitial positions 4a, 32f3, 96j1 and 96k1. The symmetry analysis in the frame of the theory of space groups and their representation gives the opportunity to find all possible transformations from high symmetry parent structure to the structures with symmetry belonging to one of its subgroups. For a given transformation it indicates possible displacements of atoms from initial positions in the parent structure, ordering of hydrogen over interstitial sites and also ordering of magnetic moments, described by the smallest possible number of free parameters. The analysis was carried out by means of the MODY computer program for vectors k = (0; 0; 0) and k = (0; 0; 1) describing the changes of translational symmetry and all positions occupied by the R, M and D atoms.

Cocrystals of 5-fluorocytosine. I. Coformers with fixed hydrogen-bonding sites.

PubMed

Tutughamiarso, Maya; Wagner, Guido; Egert, Ernst

2012-08-01

The antifungal drug 5-fluorocytosine (4-amino-5-fluoro-1,2-dihydropyrimidin-2-one) was cocrystallized with five complementary compounds in order to better understand its drug-receptor interaction. The first two compounds, 2-aminopyrimidine (2-amino-1,3-diazine) and N-acetylcreatinine (N-acetyl-2-amino-1-methyl-5H-imidazol-4-one), exhibit donor-acceptor sites for R(2)(2)(8) heterodimer formation with 5-fluorocytosine. Such a heterodimer is observed in the cocrystal with 2-aminopyrimidine (I); in contrast, 5-fluorocytosine and N-acetylcreatinine [which forms homodimers in its crystal structure (II)] are connected only by a single hydrogen bond in (III). The other three compounds 6-aminouracil (6-amino-2,4-pyrimidinediol), 6-aminoisocytosine (2,6-diamino-3H-pyrimidin-4-one) and acyclovir [acycloguanosine or 2-amino-9-[(2-hydroxyethoxy)methyl]-1,9-dihydro-6H-purin-6-one] possess donor-donor-acceptor sites; therefore, they can interact with 5-fluorocytosine to form a heterodimer linked by three hydrogen bonds. In the cocrystals with 6-aminoisocytosine (Va)-(Vd), as well as in the cocrystal with the antiviral drug acyclovir (VII), the desired heterodimers are observed. However, they are not formed in the cocrystal with 6-aminouracil (IV), where the components are connected by two hydrogen bonds. In addition, a solvent-free structure of acyclovir (VI) was obtained. A comparison of the calculated energies released during dimer formation helped to rationalize the preference for hydrogen-bonding interactions in the various cocrystal structures.

Design of ferrocene-dipeptide bioorganometallic conjugates to induce chirality-organized structures.

PubMed

Moriuchi, Toshiyuki; Hirao, Toshikazu

2010-07-20

The highly ordered molecular assemblies in proteins can have a variety of functions, as observed in enzymes, receptors, and the like. Synthetic scientists are constructing bioinspired systems by harnessing the self-assembling properties of short peptides. Secondary structures such as alpha-helices, beta-sheets, and beta-turns are important in protein folding, which is mostly directed and stabilized by hydrogen bonding and the hydrophobic interactions of side chains. The design of secondary structure mimics that are composed of short peptides has attracted much attention, both for gaining fundamental insight into the factors affecting protein folding and for developing pharmacologically useful compounds, artificial receptors, asymmetric catalysts, and new materials. Ferrocenes are an organometallic scaffold with a central reverse-turn unit based on the inter-ring spacing of about 3.3 A, which is a suitable distance for hydrogen bonding between attached peptide strands. The conjugation of organometallic compounds with biomolecules such as amino acids, peptides, and DNA should provide novel systems that reflect properties of both the ferrocene and the biologically derived moieties. In this Account, we focus on recent advances in the design of ferrocene-peptide bioconjugates, which help illustrate the peptidomimetic basis for protein folding and the means of constructing highly ordered molecular assemblies. Ferrocene-peptide bioconjugates are constructed to form chirality-organized structures in both solid and solution states. The ferrocene serves as a reliable organometallic scaffold for the construction of protein secondary structures via intramolecular hydrogen bonding: the attached dipeptide strands are constrained within the appropriate dimensions. The introduction of the chiral dipeptide chains into the ferrocene scaffold induces the conformational enantiomerization of the ferrocenyl moiety; the chirality-organized structure results from intramolecular hydrogen bonding. The configuration and sequence of the amino acids are instrumental in the process. Regulation of the directionality and specificity of hydrogen bonding is a key component in the design of various molecular assemblies. Ferrocene-peptide bioconjugates also have a strong tendency to self-assemble through the contributions of available hydrogen-bonding donors in the solid state. Some ferrocene-peptide bioconjugates bearing only one dipeptide chain exhibit a helically ordered molecular assembly through a network of intermolecular (rather than intramolecular) hydrogen bonds. The propensity to form the chiral helicity appears to be controlled by the chirality of the dipeptide chains. Organization of host molecules is a useful strategy for forming artificial receptors. The conformationally regulated ferrocene-peptide bioconjugate provides the chirality-organized binding site for size-selective and chiral recognition of dicarboxylic acids through multipoint hydrogen bonds. Metal ions serve a variety of purposes in proteins, including structural stabilization for biological function. The complexation of ferrocene-peptide bioconjugates with palladium(II) compounds not only stabilizes the chirality conformational regulation but also induces conformational regulation of the dipeptide chain through complexation and intramolecular chirality organization. Construction of the chirality-organized ferrocene-peptide bioconjugates is also achieved by metal-directed assembly. These varied examples amply demonstrate the value of ferrocene-peptide bioconjugates in asserting architectural control over highly ordered molecular assemblies.

N-tert-Butyl-N'-(5,7-dimethyl-1,8-naphthyridin-2-yl)urea.

PubMed

Lüning, U; Kühl, C; Bolte, M

2001-08-01

The title compound, C(15)H(20)N(4)O, has been synthesized as an AADD recognition unit for quadruple hydrogen bonds. All non-H atoms of the molecule apart from two methyl groups of the tert-butyl group lie in a common plane. An intramolecular hydrogen bond is formed connecting two N atoms. In the solid state, the title compound crystallizes as a centrosymmetric dimer connected by N-H...O=C interactions with an N...O distance of 2.824 (2) A.

Optimization of on-line hydrogen stable isotope ratio measurements of halogen- and sulfur-bearing organic compounds using elemental analyzer–chromium/high-temperature conversion isotope ratio mass spectrometry (EA-Cr/HTC-IRMS)

USGS Publications Warehouse

Gehre, Matthias; Renpenning, Julian; Geilmann, Heike; Qi, Haiping; Coplen, Tyler B.; Kümmel, Steffen; Ivdra, Natalija; Brand, Willi A.; Schimmelmann, Arndt

2017-01-01

Conclusions: The optimized EA-Cr/HTC reactor design can be implemented in existing analytical equipment using commercially available material and is universally applicable for both heteroelement-bearing and heteroelement-free organic-compound classes. The sensitivity and simplicity of the on-line EA-Cr/HTC-IRMS technique provide a much needed tool for routine hydrogen-isotope source tracing of organic contaminants in the environment. Copyright © 2016 John Wiley & Sons, Ltd.

Structural Analogues of Selfotel.

PubMed

Dziuganowska, Zofia A; Ślepokura, Katarzyna; Volle, Jean-Noël; Virieux, David; Pirat, Jean-Luc; Kafarski, Paweł

2016-06-17

A small library of phosphonopiperidylcarboxylic acids, analogues of NMDA antagonist selfotel (CGS 19755), was synthesized. First, the series of aromatic esters was obtained via a palladium-catalyzed cross-coupling reaction (Hirao coupling) of dialkyl phosphites with bromopyridinecarboxylates, followed by their hydrolysis. Then, hydrogenation of the resulting phosphonopyridylcarboxylic acids over PtO2 yielded the desired phosphonopiperidylcarboxylic acids. NMR studies indicated that the hydrogenation reaction proceeds predominantly by cis addition. Several compounds were obtained as monocrystal structures. Preliminary biological studies performed on cultures of neurons suggest that the obtained compounds possess promising activity toward NMDA receptors.

Generation of semicarbazide from natural azine development in foods, followed by reaction with urea compounds.

PubMed

Abernethy, Grant A

2015-01-01

This paper proposes a mechanism to explain the trace levels of natural semicarbazide occasionally observed in foods. The analytical derivative of semicarbazide, 2-nitrobenzaldehyde semicarbazone, is often measured as a metabolite marker to detect the widely banned antibiotic nitrofurazone. However, this marker is not specific as semicarbazide may be present in foods for several reasons other than exposure to nitrofurazone. In some cases, an entirely natural origin of semicarbazide is suspected, although up until now there was no explanation about how semicarbazide could occur naturally. In this work, semicarbazide is proposed as being generated from natural food compounds via an azine intermediate. Hydrazine, in the form of azines or hydrazones, may be generated in dilute aqueous solution from the natural food compounds ammonia, hydrogen peroxide and acetone, following known oxidation chemistry. When this mixture was prepared in the presence of ureas such as allantoin, urea, biuret or hydroxyurea, and then analysed by the standard method for the determination of semicarbazide, 2-nitrobenzaldehyde semicarbazone was detected. 2-Nitrobenzaldehyde aldazine was also found, and it may be a general marker for azines in foods. This proposal, that azine formation is central to semicarbazide development, provides a convergence of the published mechanisms for semicarbazide. The reaction starts with hydrogen peroxide, peracetic acid, atmospheric oxygen or hypochlorite; generates hydrazine either by an oxaziridine intermediate or via the chlorination of ammonia; and then either route may converge on azine formation, followed by reaction with a urea compound. Additionally, carbamate ion may speculatively generate semicarbazide by reaction with hydrazine, which might be a significant route in the case of the hypochlorite treatment of foods or food contact surfaces. Significantly, detection of 2-nitrobenzaldehyde semicarbazone may be somewhat artefactual because semicarbazide can form during the acid conditions of analysis, which can free hydrazine in the presence of urea compounds.

Hydrogen bonding interactions and supramolecular assemblies in 2-amino guanidinium 4-methyl benzene sulphonate crystal structure: Hirshfeld surfaces and computational calculations

NASA Astrophysics Data System (ADS)

Muthuraja, P.; Joselin Beaula, T.; Balachandar, S.; Bena Jothy, V.; Dhandapani, M.

2017-10-01

2-aminoguanidinium 4-methyl benzene sulphonate (AGMS), an organic compound with big assembly of hydrogen bonding interactions was crystallized at room temperature. The structure of the compound was confirmed by FT-IR, NMR and single crystal X-ray diffraction analysis. Numerous hydrogen bonded interactions were found to form supramolecular assemblies in the molecular structure. Fingerprint plots of Hirshfeld surface analysis spells out the interactions in various directions. The molecular structure of AGMS was optimised by HF, MP2 and DFT (B3LYP and CAM-B3LYP) methods at 6-311G (d,p) basis set and the geometrical parameters were compared. Electrostatic potential calculations of the reactants and product confirm the transfer of proton. Optical properties of AGMS were ascertained by UV-Vis absorbance and reflectance spectra. The band gap of AGMS is found to be 2.689 eV. Due to numerous hydrogen bonds, the crystal is thermally stable up to 200 °C. Hyperconjugative interactions which are responsible for the second hyperpolarizabilities were accounted by NBO analysis. Static and frequency dependent optical properties were calculated at HF and DFT methods. The hyperpolarizabilities of AGMS increase rapidly at frequencies 0.0428 and 0.08 a.u. compared to static one. The compound exhibits violet and blue emission.

Hydrogen production by the hyperthermophilic bacterium Thermotoga maritima Part II: modeling and experimental approaches for hydrogen production.

PubMed

Auria, Richard; Boileau, Céline; Davidson, Sylvain; Casalot, Laurence; Christen, Pierre; Liebgott, Pierre Pol; Combet-Blanc, Yannick

2016-01-01

Thermotoga maritima is a hyperthermophilic bacterium known to produce hydrogen from a large variety of substrates. The aim of the present study is to propose a mathematical model incorporating kinetics of growth, consumption of substrates, product formations, and inhibition by hydrogen in order to predict hydrogen production depending on defined culture conditions. Our mathematical model, incorporating data concerning growth, substrates, and products, was developed to predict hydrogen production from batch fermentations of the hyperthermophilic bacterium, T. maritima . It includes the inhibition by hydrogen and the liquid-to-gas mass transfer of H 2 , CO 2 , and H 2 S. Most kinetic parameters of the model were obtained from batch experiments without any fitting. The mathematical model is adequate for glucose, yeast extract, and thiosulfate concentrations ranging from 2.5 to 20 mmol/L, 0.2-0.5 g/L, or 0.01-0.06 mmol/L, respectively, corresponding to one of these compounds being the growth-limiting factor of T. maritima . When glucose, yeast extract, and thiosulfate concentrations are all higher than these ranges, the model overestimates all the variables. In the window of the model validity, predictions of the model show that the combination of both variables (increase in limiting factor concentration and in inlet gas stream) leads up to a twofold increase of the maximum H 2 -specific productivity with the lowest inhibition. A mathematical model predicting H 2 production in T. maritima was successfully designed and confirmed in this study. However, it shows the limit of validity of such mathematical models. Their limit of applicability must take into account the range of validity in which the parameters were established.

Polymer formulation for removing hydrogen and liquid water from an enclosed space

DOEpatents

Shepodd, Timothy J [Livermore, CA

2006-02-21

This invention describes a solution to the particular problem of liquid water formation in hydrogen getters exposed to quantities of oxygen. Water formation is usually desired because the recombination reaction removes hydrogen without affecting gettering capacity and the oxygen removal reduces the chances for a hydrogen explosion once free oxygen is essentially removed. The present invention describes a getter incorporating a polyacrylate compound that can absorb up to 500% of its own weight in liquid water without significantly affecting its hydrogen gettering/recombination properties, but that also is insensitive to water vapor.

Method and system for storing and generating hydrogen

NASA Technical Reports Server (NTRS)

Kindler, Andrew (Inventor); Narayanan, Sri R. (Inventor); Huang, Yuhong (Inventor)

2011-01-01

A method and system for storing and generating hydrogen. The method comprises generating hydrogen and heat from the reaction of a metal or metal compound with water. The heat generated from this reaction may then be converted to other forms of energy such as by passing the heat through a thermal electric device to recover electrical energy for storage in a battery. In an alternative and preferred embodiment, the heat is used to drive additional reactions for generating more hydrogen and is preferably used to drive an endothermic dehydrogenation reaction resulting in increased hydrogen generation and consumption of the heat.

An X-ray crystallographic and density functional theory study of (3Z)-4-(5-ethylsulfonyl-2-hydroxyanilino)pent-3-en-2-one and (3Z)-4-(5-tert-butyl-2-hydroxyanilino)pent-3-en-2-one.

PubMed

Akerman, Kate J; Munro, Orde Q

2013-03-01

The Schiff base enaminones (3Z)-4-(5-ethylsulfonyl-2-hydroxyanilino)pent-3-en-2-one, C13H17NO4S, (I), and (3Z)-4-(5-tert-butyl-2-hydroxyanilino)pent-3-en-2-one, C15H21NO2, (II), were studied by X-ray crystallography and density functional theory (DFT). Although the keto tautomer of these compounds is dominant, the O=C-C=C-N bond lengths are consistent with some electron delocalization and partial enol character. Both (I) and (II) are nonplanar, with the amino-phenol group canted relative to the rest of the molecule; the twist about the N(enamine)-C(aryl) bond leads to dihedral angles of 40.5 (2) and -116.7 (1)° for (I) and (II), respectively. Compound (I) has a bifurcated intramolecular hydrogen bond between the N-H group and the flanking carbonyl and hydroxy O atoms, as well as an intermolecular hydrogen bond, leading to an infinite one-dimensional hydrogen-bonded chain. Compound (II) has one intramolecular hydrogen bond and one intermolecular C=O...H-O hydrogen bond, and consequently also forms a one-dimensional hydrogen-bonded chain. The DFT-calculated structures [in vacuo, B3LYP/6-311G(d,p) level] for the keto tautomers compare favourably with the X-ray crystal structures of (I) and (II), confirming the dominance of the keto tautomer. The simulations indicate that the keto tautomers are 20.55 and 18.86 kJ mol(-1) lower in energy than the enol tautomers for (I) and (II), respectively.

Magnetic behavior of R2Fe14B hydrides (R = Gd, Tb, Dy, Ho and Er)

NASA Astrophysics Data System (ADS)

Zhang, L. Y.; Pourarian, F.; Wallace, W. E.

1988-01-01

R 2Fe 14B systems, with R = Gd, Tb, By, HoandEr were hydrogenated to the composition R 2Fe 14BH x where x ranges from 3.7 to 5.4. The pressure-composition isotherms (PCIs) of the hydrides showed only a solid solution behavior. No plateau pressure region was observed between room temperature and 300° C and at pressures down to 10 -2 atm. The absorbed hydrogen leads to an increase of 2.6 to 3.4% in unit cell volume, without a change in crystal structure. Magnetic characteristics of the present compounds were investigated over the temperature range 4.2 to 1100 K and at applied field up to 20 kOe. Saturation magnetization, Ms, and magnetic ordering temperature, Tc, were enhanced upon hydrogenation. Tc, is found to be dependent on the hydriding composition. Hydrogen induces a spin-reorientation effect (SR) in Gd- and Dy-containing compounds, while it has a marked influence in raising the spin-reorientation temperature, TSR, in the Er 2Fe 14B compound. The hydride involving Tb appears to remain uniaxial to the lowest temperature studied. In all cases the anisotropy fields, HA/' were significally reduced by hydrogen absorption. These varied magnetic behaviors can be ascribed to the effects: (1) variations in the interatomic distances, (2) strengthening the 3d-3d and weakening the 4f-3d exchange interactions and (3) the interstitial site occupations of hydrogen in the lattice. The spin-reorientation phenomena observed for Gd 2Fe 14BH x suggest that there is competition among the 6 Fe sublattices in regard to the sign and temperature coefficient of anisotropy.

D/H isotope ratios of kerogen, bitumen, oil, and water in hydrous pyrolysis of source rocks containing kerogen types I, II, IIS, and III

USGS Publications Warehouse

Schimmelmann, A.; Lewan, M.D.; Wintsch, R.P.

1999-01-01

Immature source rock chips containing different types of kerogen (I, II, IIS, III) were artificially matured in isotopically distinct waters by hydrous pyrolysis and by pyrolysis in supercritical water. Converging isotopic trends of inorganic (water) and organic (kerogen, bitumen, oil) hydrogen with increasing time and temperature document that water-derived hydrogen is added to or exchanged with organic hydrogen, or both, during chemical reactions that take place during thermal maturation. Isotopic mass-balance calculations show that, depending on temperature (310-381??C), time (12-144 h), and source rock type, between ca. 45 and 79% of carbon-bound hydrogen in kerogen is derived from water. Estimates for bitumen and oil range slightly lower, with oil-hydrogen being least affected by water-derived hydrogen. Comparative hydrous pyrolyses of immature source rocks at 330??C for 72 h show that hydrogen in kerogen, bitumen, and expelled oil/wax ranks from most to least isotopically influenced by water-derived hydrogen in the order IIS > II ~ III > I. Pyrolysis of source rock containing type II kerogen in supercritical water at 381 ??C for 12 h yields isotopic results that are similar to those from hydrous pyrolysis at 350??C for 72 h, or 330??C for 144 h. Bulk hydrogen in kerogen contains several percent of isotopically labile hydrogen that exchanges fast and reversibly with hydrogen in water vapor at 115??C. The isotopic equilibration of labile hydrogen in kerogen with isotopic standard water vapors significantly reduces the analytical uncertainty of D/H ratios when compared with simple D/H determination of bulk hydrogen in kerogen. If extrapolation of our results from hydrous pyrolysis is permitted to natural thermal maturation at lower temperatures, we suggest that organic D/H ratios of fossil fuels in contact with formation waters are typically altered during chemical reactions, but that D/H ratios of generated hydrocarbons are subsequently little or not affected by exchange with water hydrogen at typical reservoir conditions over geologic time. It will be difficult to utilize D/H ratios of thermally mature bulk or fractions of organic matter to quantitatively reconstruct isotopic aspects of paleoclimate and paleoenvironment. Hope resides in compound-specific D/H ratios of thermally stable, extractable biomarkers ('molecular fossils') that are less susceptible to hydrogen exchange with water-derived hydrogen.

Thermodynamics of hydrogen bond patterns in supramolecular assemblies of water molecules.

PubMed

Henry, Marc

2002-07-02

The PACHA (Partial Atomic Charges and Hardnesses Analysis) formalism is applied to various supramolecular assemblies of water molecules. After a detailed study of all available crystal structures for ice polymorphs, we shown that the hydrogen bond strength is roughly constant below 1 GPa and considerably weakened above that value. New hydrogen bond patterns are proposed for ice IV, V, and VI after (EB) (electrostatic balance) minimization. For other polymorphs, there is an almost perfect coincidence between experimental and predicted hydrogen bond patterns. The evolution of hydrogen bond energy as a function of molecular geometry in water clusters with up to 280 water molecules and in large supramolecular compounds is quantitatively described. Intermolecular hydrogen bonds are found to lie between -9 and -32 kJ mol-1, the stronger interaction occurs within the spherical fully disordered water droplet buried at the heart of Müller's superfullerene keplerate. The weakest one occurs in a chiral molecular snub cube built from six calix[4]resorcinarene and eight water molecules. Intramolecular hydrogen bonds are found in the range -10-100 kJ mol-1 and can thus be considerably stronger than intermolecular bonds. Finally, through the investigation of a clathrate type I compound, it was possible to obtain a deep insight of the host-guest interactions and self-assembly rules of water cages in these materials.

Hydrogen peroxide as a new defensive compound in "benzoyl cyanide" producing polydesmid millipedes

NASA Astrophysics Data System (ADS)

Kuwahara, Yasumasa; Yamaguchi, Takuya; Ichiki, Yayoi; Tanabe, Tsutomu; Asano, Yasuhisa

2017-04-01

Hydrogen peroxide was newly and simultaneously demonstrated with well-known hydrogen cyanide as a component of defensive secretions of "benzoyl cyanide" producing polydesmid millipedes. Presence of hydrogen peroxide was successively evidenced by Trinder reagent's spray with colorless as well as oily smears of defensive secretions containing benzoyl cyanide and hydrogen cyanide by alkaline picrate paper treatment. Linear correlation was demonstrated between quantities of hydrogen peroxide and benzoyl cyanide. By qualitative assay, seven benzoyl cyanide containing polydesmidans (six species of adults and one species of a nymph at stadium I) tested positive to Trinder reagent, indicative of the presence of hydrogen peroxide (together with hydrogen cyanide), while two cyanogenic species without benzoyl cyanide exhibited negative responses to the reagent. Two types of millipedes were elucidated as species of cyanogenic Polydesmida.

Hydrogen peroxide as a new defensive compound in "benzoyl cyanide" producing polydesmid millipedes.

PubMed

Kuwahara, Yasumasa; Yamaguchi, Takuya; Ichiki, Yayoi; Tanabe, Tsutomu; Asano, Yasuhisa

2017-04-01

Hydrogen peroxide was newly and simultaneously demonstrated with well-known hydrogen cyanide as a component of defensive secretions of "benzoyl cyanide" producing polydesmid millipedes. Presence of hydrogen peroxide was successively evidenced by Trinder reagent's spray with colorless as well as oily smears of defensive secretions containing benzoyl cyanide and hydrogen cyanide by alkaline picrate paper treatment. Linear correlation was demonstrated between quantities of hydrogen peroxide and benzoyl cyanide. By qualitative assay, seven benzoyl cyanide containing polydesmidans (six species of adults and one species of a nymph at stadium I) tested positive to Trinder reagent, indicative of the presence of hydrogen peroxide (together with hydrogen cyanide), while two cyanogenic species without benzoyl cyanide exhibited negative responses to the reagent. Two types of millipedes were elucidated as species of cyanogenic Polydesmida.

Photochemical dimerization of organic compounds

DOEpatents

Crabtree, Robert H.; Brown, Stephen H.; Muedas, Cesar A.; Ferguson, Richard R.

1992-01-01

At least one of selectivity and reaction rate of photosensitized vapor phase dimerizations, including dehydrodimerizations, hydrodimerizations and cross-dimerizations of saturated and unsaturated organic compounds is improved by conducting the dimerization in the presence of hydrogen or nitrous oxide.

Tantalum-containing catalyst useful for producing alcohols from synthesis gas

DOEpatents

Kinkade, Nancy E.

1991-01-01

A catalyst useful for selectively converting a mixture of carbon monoxide and hydrogen to a mixture of lower alkanols consisting essentially of a mixture of molybdenum sulfide, an alkali metal compound and a tantalum compound.

Tantalum-containing catalyst useful for producing alcohols from synthesis gas

DOEpatents

Kinkade, Nancy E.

1992-01-01

A catalyst useful for selectively converting a mixture of carbon monoxide and hydrogen to a mixture of lower alkanols consisting essentially of a mixture of molybdenum sulfide, an alkali metal compound and a tantalum compound.

Crystal structures of hibiscus acid and hibiscus acid dimethyl ester isolated from Hibiscus sabdariffa (Malvaceae).

PubMed

Zheoat, Ahmed M; Gray, Alexander I; Igoli, John O; Kennedy, Alan R; Ferro, Valerie A

2017-09-01

The biologically active title compounds have been isolated from Hibiscus sabdariffa plants, hibiscus acid as a dimethyl sulfoxide monosolvate [systematic name: (2 S ,3 R )-3-hy-droxy-5-oxo-2,3,4,5-tetra-hydro-furan-2,3-di-carb-oxy-lic acid dimethyl sulfoxide monosolvate], C 6 H 6 O 7 ·C 2 H 6 OS, (I), and hibiscus acid dimethyl ester [systematic name: dimethyl (2 S ,3 R )-3-hy-droxy-5-oxo-2,3,4,5-tetra-hydro-furan-2,3-di-carboxyl-ate], C 8 H 10 O 7 , (II). Compound (I) forms a layered structure with alternating layers of lactone and solvent mol-ecules, that include a two-dimensional hydrogen-bonding construct. Compound (II) has two crystallographically independent and conformationally similar mol-ecules per asymmetric unit and forms a one-dimensional hydrogen-bonding construct. The known absolute configuration for both compounds has been confirmed.

Application of Atmospheric Pressure Photoionization H/D-exchange Mass Spectrometry for Speciation of Sulfur-containing Compounds.

PubMed

Acter, Thamina; Kim, Donghwi; Ahmed, Arif; Ha, Ji-Hyoung; Kim, Sunghwan

2017-08-01

Herein we report the observation of atmospheric pressure in-source hydrogen-deuterium exchange (HDX) of thiol group for the first time. The HDX for thiol group was optimized for positive atmospheric pressure photoionization (APPI) mass spectrometry (MS). The optimized HDX-MS was applied for 31 model compounds (thiols, thiophenes, and sulfides) to demonstrate that exchanged peaks were observed only for thiols. The optimized method has been successfully applied to the isolated fractions of sulfur-rich oil samples. The exchange of one and two thiol hydrogens with deuterium was observed in the thiol fraction; no HDX was observed in the other fractions. Thus, the results presented in this study demonstrate that the HDX-MS method using APPI ionization source can be effective for speciation of sulfur compounds. This method has the potential to be used to access corrosion problems caused by thiol-containing compounds. Graphical Abstract ᅟ.

Radio- and photosensitization of DNA with compounds containing platinum and bromine atoms

NASA Astrophysics Data System (ADS)

Śmiałek, Małgorzata A.; Ptasińska, Sylwia; Gow, Jason; Vrønning Hoffmann, Søren; Mason, Nigel J.

2015-05-01

Irradiations of plasmid DNA by both X-rays and UV light in the presence and absence of compounds containing platinum and bromine atoms were performed in order to asses the sensitization potential of these compounds. Plasmid DNA pBR322 was incubated with platinum (II) bromide, hydrogen hexabromoplatinate (IV), hydrogen hexahydroxyplatinate (IV) and sodium hexahydroxyplatinate (IV). Incubation was followed by X-ray or UV irradiations. It was found that amongst the sensitizers tested, during irradiations carried out in the presence of platinum (II) bromide, the highest levels of double strand breaks formation upon X-ray treatment were recorded. In contrast much less damage was induced by UV light. Data presented here suggests that this compound may be a promising radiosensitizer for cancer treatment. Contribution to the Topical Issue "COST Action Nano-IBCT: Nano-scale Processes Behind Ion-Beam Cancer Therapy", edited by Andrey Solov'yov, Nigel Mason, Gustavo García, Eugene Surdutovich.

Magnetic Carbon Supported Palladium Nanoparticles: An Efficient and Sustainable Catalyst for Hydrogenation Reactions

EPA Science Inventory

Magnetic carbon supported Pd catalyst has been synthesized via in situ generation of nanoferrites and incorporation of carbon from renewable cellulose via calcination; the catalyst can be used for the hydrogenation of alkenes and reduction of aryl nitro compounds.

SUMMARY REVIEW OF HEALTH EFFECTS ASSOCIATED WITH HYDROGEN FLUORIDE AND RELATED COMPOUNDS: HEALTH ISSUE ASSESSMENT

EPA Science Inventory

The major natural sources of airborne hydrogen fluoride (HF) are volcanic activity, ocean spray, and crustal weathering of fluoride-containing rocks. Anthropogenic sources include emissions from industrial operations such as aluminum and fluorocarbon production, and uranium proce...

Hydrolysis of ammonia borane as a hydrogen source: fundamental issues and potential solutions towards implementation.

PubMed

Sanyal, Udishnu; Demirci, Umit B; Jagirdar, Balaji R; Miele, Philippe

2011-12-16

In today's era of energy crisis and global warming, hydrogen has been projected as a sustainable alternative to depleting CO(2)-emitting fossil fuels. However, its deployment as an energy source is impeded by many issues, one of the most important being storage. Chemical hydrogen storage materials, in particular B-N compounds such as ammonia borane, with a potential storage capacity of 19.6 wt % H(2) and 0.145 kg(H2)L(-1), have been intensively studied from the standpoint of addressing the storage issues. Ammonia borane undergoes dehydrogenation through hydrolysis at room temperature in the presence of a catalyst, but its practical implementation is hindered by several problems affecting all of the chemical compounds in the reaction scheme, including ammonia borane, water, borate byproducts, and hydrogen. In this Minireview, we exhaustively survey the state of the art, discuss the fundamental problems, and, where applicable, propose solutions with the prospect of technological applications. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hydrogen and syngas production by catalytic gasification of algal biomass (Cladophora glomerata L.) using alkali and alkaline-earth metals compounds.

PubMed

Ebadi, Abdol Ghaffar; Hisoriev, Hikmat; Zarnegar, Mohammad; Ahmadi, Hamed

2018-01-02

The steam gasification of algal biomass (Cladophora glomerata L.) in presence of alkali and alkaline-earth metal compounds catalysts was studied to enhance the yield of syngas and reduce its tar content through cracking and reforming of condensable fractions. The commercial catalysts used include NaOH, KHCO 3 , Na 3 PO 4 and MgO. The gasification runs carried out with a research scale, biomass gasification unit, show that the NaOH has a strong potential for production of hydrogen, along with the added advantages of char converting and tar destruction, allowing enhancement of produced syngas caloric value. When the temperature increased from 700°C to 900°C, the tar content in the gas sharply decreased, while the hydrogen yield increased. Increasing steam/biomass ratio significantly increased hydrogen yield and tar destruction; however, the particle size in the range of 0.5-2.5 mm played a minor role in the process.

[Spectroscopic Study of Salbutamol Molecularly Imprinted Polymers].

PubMed

Ren, Hui-peng; Guan, Yu-yu; Dai, Rong-hua; Liu, Guo-yan; Chai, Chun-yan

2016-02-01

In order to solve the problem of on-site rapid detection of salbutamol residues in feed and animal products, and develop a new method of fast detection of salbutamol on the basis of the molecular imprinting technology, this article uses the salbutamol (SAL) working as template molecule, methacrylic acid (MAA) working as functional monomer. On this basis, a new type of core-shell type salbutamol molecularly imprinted polymers were prepared with colloidal gold particles as triggering core. Superficial characteristics of the MIPs and the related compounds were investigated by ultraviolet (UV) spectra and infrared (IR) spectra, Raman spectra, Scanning electron microscopy (SEM) respectively. The results indicated that a stable hydrogen bonding complex has been formed between the carboxyl groups of SAL and MA with a matching ratio of 1:1. The complex can be easily eluted by the reagent containing hydrogen bonding. The chemical binding constant K reaches -0.245 x 10⁶ L² · mol⁻². The possible binding sites of the hydrogen bonding was formed between the hydrogen atoms of -COOH in MA and the oxygen atoms of C==O in SAL. IR and Raman spectrum showed that, compared with MA, a significant red shift of -OH absorption peak was manifested in MIPs, which proved that SAL as template molecule occurred a specific bond between MA. Red shift of stretching vibration absorption peak of C==O was also detected in the un-eluted MIPs and obvious energy loss happened, which demonstrated a possible binding sites is SAL intramolecular of C==O atom of oxygen. If the hydrogen atoms of -COOH in MA wanted to generate hydrogen bond. However, the shapes of absorption peak of other functional groups including C==C, C==O, and -OH were very similar both in MIPs and NIPs. Specific cavities were formed after the template molecules in MIPs were removed. It was proved by the adsorption experiment that the specific sites in these cavities highly match with the chemical and space structure of SAL. Besides, colloidal gold type core-shell molecularly imprinted polymers have looser surface, more cavities in the surface compared with ordinary molecularly imprinted polymers, which increased the effective area of adsorption to target molecules. So it have better performance in adsorption. Based on the principle that these cavities can specificly recognize and combine with target molecule in the test sample, and the excellent ability of colloidal gold core-shell molecularly imprinted polymers, the development of novel methods for fast determination of SAL based on the molecular imprinting technology can be expected in the near future.

A theoretical study of the hydrogen-storage potential of (H2)4CH4 in metal organic framework materials and carbon nanotubes.

PubMed

Li, Q; Thonhauser, T

2012-10-24

The hydrogen-methane compound (H(2))(4)CH(4)-or for short H4M-is one of the most promising hydrogen-storage materials. This van der Waals compound is extremely rich in molecular hydrogen: 33.3 mass%, not including the hydrogen bound in CH(4); including it, we reach even 50.2 mass%. Unfortunately, H4M is not stable under ambient pressure and temperature, requiring either low temperature or high pressure. In this paper, we investigate the properties and structure of the molecular and crystalline forms of H4M, using ab initio methods based on van der Waals DFT (vdW-DF). We further investigate the possibility of creating the pressures required to stabilize H4M through external agents such as metal organic framework (MOF) materials and carbon nanotubes, with very encouraging results. In particular, we find that certain MOFs can create considerable pressure for H4M in their cavities, but not enough to stabilize it at room temperature, and moderate cooling is still necessary. On the other hand, we find that all the investigated carbon nanotubes can create the high pressures required for H4M to be stable at room temperature, with direct implications for new and exciting hydrogen-storage applications.

Hydrogen-fluorine exchange in NaBH4-NaBF4.

PubMed

Rude, L H; Filsø, U; D'Anna, V; Spyratou, A; Richter, B; Hino, S; Zavorotynska, O; Baricco, M; Sørby, M H; Hauback, B C; Hagemann, H; Besenbacher, F; Skibsted, J; Jensen, T R

2013-11-07

Hydrogen-fluorine exchange in the NaBH4-NaBF4 system is investigated using a range of experimental methods combined with DFT calculations and a possible mechanism for the reactions is proposed. Fluorine substitution is observed using in situ synchrotron radiation powder X-ray diffraction (SR-PXD) as a new Rock salt type compound with idealized composition NaBF2H2 in the temperature range T = 200 to 215 °C. Combined use of solid-state (19)F MAS NMR, FT-IR and DFT calculations supports the formation of a BF2H2(-) complex ion, reproducing the observation of a (19)F chemical shift at -144.2 ppm, which is different from that of NaBF4 at -159.2 ppm, along with the new absorption bands observed in the IR spectra. After further heating, the fluorine substituted compound becomes X-ray amorphous and decomposes to NaF at ~310 °C. This work shows that fluorine-substituted borohydrides tend to decompose to more stable compounds, e.g. NaF and BF3 or amorphous products such as closo-boranes, e.g. Na2B12H12. The NaBH4-NaBF4 composite decomposes at lower temperatures (300 °C) compared to NaBH4 (476 °C), as observed by thermogravimetric analysis. NaBH4-NaBF4 (1:0.5) preserves 30% of the hydrogen storage capacity after three hydrogen release and uptake cycles compared to 8% for NaBH4 as measured using Sievert's method under identical conditions, but more than 50% using prolonged hydrogen absorption time. The reversible hydrogen storage capacity tends to decrease possibly due to the formation of NaF and Na2B12H12. On the other hand, the additive sodium fluoride appears to facilitate hydrogen uptake, prevent foaming, phase segregation and loss of material from the sample container for samples of NaBH4-NaF.

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

Ma, Ning; Guo, Wei-Ying; Song, Hui-Hua, E-mail: songhuihua@mail.hebtu.edu.cn

Five new Cd(II) coordination polymers with N-benzoyl-L-glutamic acid (H{sub 2}bzgluO) and different N-donor ligands, [Cd(bzgluO)(2,2′-bipy)(H{sub 2}O)]{sub n} (1), [Cd(bzgluO)(2,4′-bipy){sub 2}(H{sub 2}O)·3H{sub 2}O]{sub n} (2), [Cd(bzgluO)(phen)·H{sub 2}O]{sub n} (3), [Cd(bzgluO)(4,4′-bipy)(H{sub 2}O)]{sub n} (4), [Cd(bzgluO)(bpp)(H{sub 2}O)·2H{sub 2}O]{sub n} (5) were synthesized (2,2′-bipy=2,2′-bipyridine, 2,4′-bipy=2,4′-bipyridine, phen=1,10-phenanthroline, 4,4′-bipy=4,4′-bipyridine, bpp=1,3-di(4-pyridyl)propane). Compounds 1–2 exhibit a 1D single-chain structure. Compound 1 generates a 2D supramolecular structure via π–π stacking and hydrogen bonding, 3D architecture of compound 2 is formed by hydrogen bonding. Compound 3 features a 1D double-chain structure, which are linked by π–π interactions into a 2D supramolecular layer. Compounds 4-5 display a 2D network structure. Neighboringmore » layers of 4 are extended into a 3D supramolecular architecture through hydrogen bonding. The structural diversity of these compounds is attributed to the effect of ancillary N-donor ligands and coordination modes of H{sub 2}bzgluO. Luminescent properties of 1–5 were studied at room temperature. Circular dichroism of compounds 1, 2 and 5 were investigated. - Graphical abstract: Five new Cd(II) metal coordination compounds with H{sub 2}bzgluO and different N-donor ligands were synthesized and characterized. Compounds 1, 2 and 3 present 1D structures, compounds 4 and 5 display 2D networks. Results indicate that auxiliary ligands and coordination modes of H{sub 2}bzgluO play an important role in governing the formation of final frameworks, and the hydrogen-bonding and π–π stacking interactions contribute the formation of the diverse supramolecular architectures. Furthermore, the different crystal structures influence the emission spectra significantly. - Highlights: • It is rarely reported that complexes prepared with N-benzoyl-L-glutamic acid. • Each complex displays diverse structures and different supramolecular interactions. • Results indicate that N-donor ligands play a crucial role in the final structures. • The different crystal structures influence the emission spectra significantly.« less

Lignin solubilization and aqueous phase reforming for the production of aromatic chemicals and hydrogen.

PubMed

Zakzeski, Joseph; Weckhuysen, Bert M

2011-03-21

The solubilization and aqueous phase reforming of lignin, including kraft, soda, and alcell lignin along with sugarcane bagasse, at low temperatures (T≤498 K) and pressures (P≤29 bar) is reported for the first time for the production of aromatic chemicals and hydrogen. Analysis of lignin model compounds and the distribution of products obtained during the lignin aqueous phase reforming revealed that lignin was depolymerized through disruption of the abundant β-O-4 linkages and, to a lesser extent, the 5-5' carbon-carbon linkages to form monomeric aromatic compounds. The alkyl chains contained on these monomeric compounds were readily reformed to produce hydrogen and simple aromatic platform chemicals, particularly guaiacol and syringol, with the distribution of each depending on the lignin source. The methoxy groups present on the aromatic rings were subject to hydrolysis to form methanol, which was also readily reformed to produce hydrogen and carbon dioxide. The composition of the isolated yields of monomeric aromatic compounds and overall lignin conversion based on these isolated yields varied from 10-15% depending on the lignin sample, with the balance consisting of gaseous products and residual solid material. Furthermore, we introduce the use of a high-pressure autoclave with optical windows and an autoclave with ATR-IR sentinel for on-line in situ spectroscopic monitoring of biomass conversion processes, which provides direct insight into, for example, the solubilization process and aqueous phase reforming reaction of lignin. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ti(Ni,Cu) pseudobinary compounds as efficient negative electrodes for Ni-MH batteries

NASA Astrophysics Data System (ADS)

Emami, Hoda; Cuevas, Fermin; Latroche, Michel

2014-11-01

The effect of Ni by Cu substitution on the structural, solid-gas and electrochemical hydrogenation properties of TiNi has been investigated. Pseudo-binary TiNi1-xCux (x ≤ 0.5) compounds have been synthesized by induction melting. They crystallize in B2 structure above 350 K and either in B19‧ (x < 0.1) or B19 (0.2 ≤ x ≤ 0.5) at room temperature (RT). For all compounds, Pressure-Composition Isotherms at 423 K exhibit a single slopping plateau pressure within the range 10-3-1 MPa of hydrogen pressure revealing a metal to hydride transformation. Both the hydrogenation capacity and the hydride stability decrease with Cu-content. The hydrided pseudobinary compounds crystallize in the tetragonal S.G. I4/mmm structure as for TiNi hydride. The electrochemical discharge capacity increases with Cu content from 150 mAh g-1 for TiNi up to 300 mAh g-1 for TiNi0.8Cu0.2 and then decreases again for larger Cu amounts. Electrochemical isotherms and in-situ neutron diffraction measurements at RT demonstrate that such a capacity increase results from a metal to hydride phase transformation in which the hydride phase is destabilized by Cu substitution. The TiNi0.8Cu0.2 compound exhibits interesting cycling stability for 30 cycles and good high-rate capability at D/2 rate. This compound has promising electrochemical properties as compared to commercial LaNi5-type alloys with the advantage of being rare-earth metal free.

Optimization of on-line hydrogen stable isotope ratio measurements of halogen- and sulfur-bearing organic compounds using elemental analyzer-chromium/high-temperature conversion isotope ratio mass spectrometry (EA-Cr/HTC-IRMS).

PubMed

Gehre, Matthias; Renpenning, Julian; Geilmann, Heike; Qi, Haiping; Coplen, Tyler B; Kümmel, Steffen; Ivdra, Natalija; Brand, Willi A; Schimmelmann, Arndt

2017-03-30

Accurate hydrogen isotopic analysis of halogen- and sulfur-bearing organics has not been possible with traditional high-temperature conversion (HTC) because the formation of hydrogen-bearing reaction products other than molecular hydrogen (H 2 ) is responsible for non-quantitative H 2 yields and possible hydrogen isotopic fractionation. Our previously introduced, new chromium-based EA-Cr/HTC-IRMS (Elemental Analyzer-Chromium/High-Temperature Conversion Isotope Ratio Mass Spectrometry) technique focused primarily on nitrogen-bearing compounds. Several technical and analytical issues concerning halogen- and sulfur-bearing samples, however, remained unresolved and required further refinement of the reactor systems. The EA-Cr/HTC reactor was substantially modified for the conversion of halogen- and sulfur-bearing samples. The performance of the novel conversion setup for solid and liquid samples was monitored and optimized using a simultaneously operating dual-detection system of IRMS and ion trap MS. The method with several variants in the reactor, including the addition of manganese metal chips, was evaluated in three laboratories using EA-Cr/HTC-IRMS (on-line method) and compared with traditional uranium-reduction-based conversion combined with manual dual-inlet IRMS analysis (off-line method) in one laboratory. The modified EA-Cr/HTC reactor setup showed an overall H 2 -recovery of more than 96% for all halogen- and sulfur-bearing organic compounds. All results were successfully normalized via two-point calibration with VSMOW-SLAP reference waters. Precise and accurate hydrogen isotopic analysis was achieved for a variety of organics containing F-, Cl-, Br-, I-, and S-bearing heteroelements. The robust nature of the on-line EA-Cr/HTC technique was demonstrated by a series of 196 consecutive measurements with a single reactor filling. The optimized EA-Cr/HTC reactor design can be implemented in existing analytical equipment using commercially available material and is universally applicable for both heteroelement-bearing and heteroelement-free organic-compound classes. The sensitivity and simplicity of the on-line EA-Cr/HTC-IRMS technique provide a much needed tool for routine hydrogen-isotope source tracing of organic contaminants in the environment. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

Investigation of supramolecular synthons and structural characterisation of aminopyridine-carboxylic acid derivatives

PubMed Central

2014-01-01

Background Co-crystal is a structurally homogeneous crystalline material that contains two or more neutral building blocks that are present in definite stoichiometric amounts. The main advantage of co-crystals is their ability to generate a variety of solid forms of a drug that have distinct physicochemical properties from the solid co-crystal components. In the present investigation, five co-crystals containing 2-amino-6-chloropyridine (AMPY) moiety were synthesized and characterized. Results The crystal structure of 2-amino-6-chloropyridine (AMPY) (I), and the robustness of pyridine-acid supramolecular synthon were discussed in four stoichiometry co-crystals of AMPY…BA (II), AMPY…2ABA (III), AMPY…3CLBA (IV) and AMPY…4NBA (V). The abbreviated designations used are benzoic acid (BA), 2-aminobenzoic acid (2ABA), 3-chlorobenzoic acid (3CLBA) and 4-nitrobenzoic acid (4NBA). All the crystalline materials have been characterized by 1HNMR, 13CNMR, IR, photoluminescence, TEM analysis and X-ray diffraction. The supramolecular assembly of each co-crystal is analyzed and discussed. Conclusions Extensive N---H · · · N/N---H · · · O/O---H · · · N hydrogen bonds are found in (I-V), featuring different supramolecular synthons. In the crystal structure, for compound (I), the 2-amino-6-chloropyridine molecules are linked together into centrosymmetric dimers by hydrogen bonds to form homosynthon, whereas for compounds (II-V), the carboxylic group of the respective acids (benzoic acid, 2-aminobenzoic acid, 3-chlorobenzoic acid and 4-nitrobenzoic acid) interacts with pyridine molecule in a linear fashion through a pair of N---H · · · O and O---H · · · N hydrogen bonds, generating cyclic hydrogen-bonded motifs with the graph-set notation R 2 2 8 , to form heterosynthon. In compound (II), another intermolecular N---H · · · O hydrogen bonds further link these heterosynthons into zig-zag chains. Whereas in compounds (IV) and (V), these heterosynthons are centrosymmetrically paired via N---H · · · O hydrogen bonds and each forms a complementary DADA [D = donor and A = acceptor] array of quadruple hydrogen bonds, with graph-set notation R238, R228 and R238. PMID:24887234

1D and 2D assembly structures by imidazole···chloride hydrogen bonds of iron(II) complexes [Fe(II)(HL(n-Pr))3]Cl·Y (HL(n-Pr) = 2-methylimidazol-4-yl-methylideneamino-n-propyl; Y = AsF6, BF4) and their spin states.

PubMed

Fujinami, Takeshi; Nishi, Koshiro; Matsumoto, Naohide; Iijima, Seiichiro; Halcrow, Malcolm A; Sunatsuki, Yukinari; Kojima, Masaaki

2011-12-07

Two Fe(II) complexes fac-[Fe(II)(HL(n-Pr))(3)]Cl·Y (Y = AsF(6) (1) and BF(4) (2)) were synthesized, where HL(n-Pr) is 2-methylimidazole-4-yl-methylideneamino-n-propyl. Each complex-cation has the same octahedral N(6) geometry coordinated by three bidentate ligands and assumes facial-isomerism, fac-[Fe(II)(HL(n-Pr))(3)](2+) with Δ- and Λ-enantiomorphs. Three imidazole groups per Δ- or Λ-fac-[Fe(II)(HL(n-Pr))(3)](2+) are hydrogen-bonded to three Cl(-) ions or, from the viewpoint of the Cl(-) ion, one Cl(-) ion is hydrogen-bonded to three neighbouring fac-[Fe(II)(HL(n-Pr))(3)](2+) cations. The 3 : 3 NH···Cl(-) hydrogen bonds between Δ- or Λ-fac-[Fe(II)(HL(n-Pr))(3)](2+) and Cl(-) generate two kinds of assembly structures. The directions of the 3 : 3 NH···Cl(-) hydrogen bonds and hence the resulting assembly structures are determined by the size of the anion Y, though Y is not involved into the network structure and just accommodated in the cavity. Compound 1 has a 1D ladder structure giving a larger cavity, in which the Δ- and Λ-fac-[Fe(II)(HL(n-Pr))(3)](2+) enantiomorphs are bridged by two NH···Cl(-) hydrogen bonds. Compound 2 has a 2D network structure with a net unit of a cyclic trimer of {fac-[Fe(II)(HL(n-Pr))(3)](2+)···Cl(-)}(3) giving a smaller cavity, in which Δ- or Λ-fac-[Fe(II)(HL(n-Pr))(3)](2+) species with the same chirality are linked by NH···Cl(-) hydrogen bonds to give a homochiral 2D network structure. Magnetic susceptibility and Mössbauer spectral measurements demonstrated that compound 1 showed an abrupt one-step spin crossover with 4.0 K thermal hysteresis of T(c↓) = 125.5 K and T(c↑) = 129.5 K and compound 2 showed no spin transition and stayed in the high-spin state over the 5-300 K temperature range.

Investigation of supramolecular synthons and structural characterisation of aminopyridine-carboxylic acid derivatives.

PubMed

Hemamalini, Madhukar; Loh, Wan-Sin; Quah, Ching Kheng; Fun, Hoong-Kun

2014-01-01

Co-crystal is a structurally homogeneous crystalline material that contains two or more neutral building blocks that are present in definite stoichiometric amounts. The main advantage of co-crystals is their ability to generate a variety of solid forms of a drug that have distinct physicochemical properties from the solid co-crystal components. In the present investigation, five co-crystals containing 2-amino-6-chloropyridine (AMPY) moiety were synthesized and characterized. The crystal structure of 2-amino-6-chloropyridine (AMPY) (I), and the robustness of pyridine-acid supramolecular synthon were discussed in four stoichiometry co-crystals of AMPY…BA (II), AMPY…2ABA (III), AMPY…3CLBA (IV) and AMPY…4NBA (V). The abbreviated designations used are benzoic acid (BA), 2-aminobenzoic acid (2ABA), 3-chlorobenzoic acid (3CLBA) and 4-nitrobenzoic acid (4NBA). All the crystalline materials have been characterized by (1)HNMR, (13)CNMR, IR, photoluminescence, TEM analysis and X-ray diffraction. The supramolecular assembly of each co-crystal is analyzed and discussed. Extensive N---H · · · N/N---H · · · O/O---H · · · N hydrogen bonds are found in (I-V), featuring different supramolecular synthons. In the crystal structure, for compound (I), the 2-amino-6-chloropyridine molecules are linked together into centrosymmetric dimers by hydrogen bonds to form homosynthon, whereas for compounds (II-V), the carboxylic group of the respective acids (benzoic acid, 2-aminobenzoic acid, 3-chlorobenzoic acid and 4-nitrobenzoic acid) interacts with pyridine molecule in a linear fashion through a pair of N---H · · · O and O---H · · · N hydrogen bonds, generating cyclic hydrogen-bonded motifs with the graph-set notation [Formula: see text] , to form heterosynthon. In compound (II), another intermolecular N---H · · · O hydrogen bonds further link these heterosynthons into zig-zag chains. Whereas in compounds (IV) and (V), these heterosynthons are centrosymmetrically paired via N---H · · · O hydrogen bonds and each forms a complementary DADA [D = donor and A = acceptor] array of quadruple hydrogen bonds, with graph-set notation [Formula: see text], [Formula: see text] and [Formula: see text].

Selective C-O Hydrogenolysis and Decarboxylation of Biomass-Derived Heterocyclic Compounds over Heterogeneous Catalysts

NASA Astrophysics Data System (ADS)

Chia, Mei

The catalytic deoxygenation of biomass-derived compounds through selective C-O hydrogenolysis, catalytic transfer hydrogenation and lactonization, and decarboxylation to value-added chemicals over heterogeneous catalysts was examined under liquid phase reaction conditions. The reactions studied involve the conversion or production of heterocyclic compounds, specifically, cyclic ethers, lactones, and 2-pyrones. A bimetallic RhRe/C catalyst was found to be selective for the hydrogenolysis of secondary C-O bonds for a broad range cyclic ethers and polyols. Results from experimentally-observed reactivity trends, NH3 temperature-programmed desorption, fructose dehydration reaction studies, and first-principles density functional theory (DFT) calculations are consistent with the hypothesis of a bifunctional catalyst which facilitates acid-catalyzed ring-opening and dehydration coupled with metal-catalyzed hydrogenation. C-O hydrogenolysis and fructose dehydration activities were observed to decrease with an increase in reduction temperature and a decrease in the number of surface metallic Re atoms measured by in situ X-ray absorption spectroscopy. No C-O hydrogenolysis activity was detected over RhRe/C under water-free conditions. The activation of water molecules by Re atoms on the surface of metallic Rh is suggested to result in the formation of Bronsted acidity over RhRe/C. The catalytic transfer hydrogenation and lactonization of levulinic acid and its esters to gamma-valerolactone was accomplished through the Meerwein-Ponndorf-Verley reaction over metal oxide catalysts using secondary alcohols as the hydrogen donor. ZrO2 was a highly active material for CTH under batch and continuous flow reaction conditions; the initial activity of the catalyst was repeatedly regenerable by calcination in air, with no observable loss in catalytic activity. Lastly, the 2-pyrone, triacetic acid lactone, is shown to be a promising biorenewable platform chemical from which a wide range of chemical intermediates and end products can be obtained using heterogeneous catalysts or by thermal decomposition. Mechanistic insights from experimentally-observed reactivity trends and results from DFT calculations indicate that 2-pyrones undergo reactions unique to their structure such as keto-enol tautomerization, retro Diels-Alder, and nucleophilic attack by water. Ring-opening and decarboxylation reactions were found to be governed by key structural features such as the degree of saturation in the ring (e.g., C4=C5 bond), nature of the solvent, and presence of an acid catalyst.

Novel hydrogen sulfide-releasing compound, S-propargyl-cysteine, prevents STZ-induced diabetic nephropathy

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

Qian, Xin; Li, Xinghui; Ma, Fenfen

2016-05-13

In this work, we demonstrated for the first time that S-propargyl-cysteine (SPRC, also named as ZYZ-802), a novel hydrogen sulfide (H{sub 2}S)-releasing compound, had renoprotective effects on streptozotocin (STZ)-induced diabetic kidney injury. SPRC treatment significantly reduced the level of creatinine, kidney to body weight ratio and in particular, markedly decreased 24-h urine microalbuminuria excretion. SPRC suppressed the mRNA expression of fibronectin and type IV collagen. In vitro, SPRC inhibited mesangial cells over-proliferation and hypertrophy induced by high glucose. Additionally, SPRC attenuated inflammation in diabetic kidneys. SPRC also reduced transforming growth factor β1 (TGF-β1) signaling and expression of phosphorylated Smad3 (p-Smad3) pathway. Moreover,more » SPRC inhibited phosphorylation of ERK, p38 protein. Taken together, SPRC was demonstrated to be a potential therapeutic candidate to suppress diabetic nephropathy. - Highlights: • We synthesized a novel hydrogen sulfide-releasing compound, S-propargyl-cysteine (SPRC). • SPRC was preliminarily demonstrated to prevent STZ-induced diabetic nephropathy (DN). • SPRC may exert potential therapeutic candidate to suppress DN.« less

Supramolecular hydrogen-bonding network in 1-(diaminomethylene)thiouron-1-ium 4-hydroxybenzenesulfonate crystal

NASA Astrophysics Data System (ADS)

Perpétuo, Genivaldo J.; Gonçalves, Rafael S.; Janczak, Jan

2015-09-01

The single crystals of 1-(diaminomethylene)thiouron-1-ium 4-hydroxybenzenesulfonate were grown using a solution growth technique. The compound crystallises in the centrosymmetric P21/c space group of the monoclinic system. The conformation of the 1-(diaminomethylene)thiouron-1-ium cation is not strictly planar, but twisted. Both arms of the cation are oppositely rotated by 8.5(1)° around the Csbnd N bonds involving the central N atom. The arrangement of oppositely charged components, i.e. 1-(diaminomethylene)thiouron-1-ium cations and 4-hydroxybenzenesulfonate anions in the crystal is mainly determined by ionic and hydrogen-bonding interactions forming supramolecular network. The possible hydrogen-bonding interactions between cation and anion units were analysed on the basis of molecular orbital calculations. The obtained deuterated analogue crystallises similar as H-compound in the monoclinic system (P21/c) with quite similar lattice parameters. The compound was also characterised by the FT-IR and Raman spectroscopies. The characteristic bands of the functional and skeletal groups of the protiated and deuterated analogue of 1-(diaminomethylene)thiouron-1-ium 4-hydroxybenzenesulfonate are discussed.

Part 2. Mechanistic aspects of the reduction of S-alkyl-thionocarbonates in the presence of triethylborane and air

PubMed Central

Allais, Florent; Boivin, Jean; Nguyen, Van Tai

2007-01-01

Experiments conducted with deuterated compounds demonstrated that during the reduction of S-alkylxanthates with triethylborane, the hydrogen atom transferred has several competing origins. Hydrogen abstraction from water (or an alcohol) is the most favourable route. PMID:18076755

A hydrogen-rich early Earth atmosphere.

PubMed

Tian, Feng; Toon, Owen B; Pavlov, Alexander A; De Sterck, H

2005-05-13

We show that the escape of hydrogen from early Earth's atmosphere likely occurred at rates slower by two orders of magnitude than previously thought. The balance between slow hydrogen escape and volcanic outgassing could have maintained a hydrogen mixing ratio of more than 30%. The production of prebiotic organic compounds in such an atmosphere would have been more efficient than either exogenous delivery or synthesis in hydrothermal systems. The organic soup in the oceans and ponds on early Earth would have been a more favorable place for the origin of life than previously thought.

Carbon material for hydrogen storage

DOEpatents

Bourlinos, Athanasios; Steriotis, Theodore; Stubos, Athanasios; Miller, Michael A

2016-09-13

The present invention relates to carbon based materials that are employed for hydrogen storage applications. The material may be described as the pyrolysis product of a molecular precursor such as a cyclic quinone compound. The pyrolysis product may then be combined with selected transition metal atoms which may be in nanoparticulate form, where the metals may be dispersed on the material surface. Such product may then provide for the reversible storage of hydrogen. The metallic nanoparticles may also be combined with a second metal as an alloy to further improve hydrogen storage performance.

Fluorination utilizing thermodynamically unstable fluorides and fluoride salts thereof

DOEpatents

Bartlett, Neil; Whalen, J. Marc; Chacon, Lisa

2000-12-12

A method for fluorinating a carbon compound or cationic carbon compound utilizes a fluorination agent selected from thermodynamically unstable nickel fluorides and salts thereof in liquid anhydrous hydrogen fluoride. The desired carbon compound or cationic organic compound to undergo fluorination is selected and reacted with the fluorination agent by contacting the selected organic or cationic organic compound and the chosen fluorination agent in a reaction vessel for a desired reaction time period at room temperature or less.

A novel liquid organic hydrogen carrier system based on catalytic peptide formation and hydrogenation

PubMed Central

Hu, Peng; Fogler, Eran; Diskin-Posner, Yael; Iron, Mark A.; Milstein, David

2015-01-01

Hydrogen is an efficient green fuel, but its low energy density when stored under high pressure or cryogenically, and safety issues, presents significant disadvantages; hence finding efficient and safe hydrogen carriers is a major challenge. Of special interest are liquid organic hydrogen carriers (LOHCs), which can be readily loaded and unloaded with considerable amounts of hydrogen. However, disadvantages include high hydrogen pressure requirements, high reaction temperatures for both hydrogenation and dehydrogenation steps, which require different catalysts, and high LOHC cost. Here we present a readily reversible LOHC system based on catalytic peptide formation and hydrogenation, using an inexpensive, safe and abundant organic compound with high potential capacity to store and release hydrogen, applying the same catalyst for loading and unloading hydrogen under relatively mild conditions. Mechanistic insight of the catalytic reaction is provided. We believe that these findings may lead to the development of an inexpensive, safe and clean liquid hydrogen carrier system. PMID:25882348

Predicting the partitioning of biological compounds between room-temperature ionic liquids and water by means of the solvation-parameter model.

PubMed

Padró, Juan M; Ponzinibbio, Agustín; Mesa, Leidy B Agudelo; Reta, Mario

2011-03-01

The partition coefficients, P(IL/w), for different probe molecules as well as for compounds of biological interest between the room-temperature ionic liquids (RTILs) 1-butyl-3-methylimidazolium hexafluorophosphate, [BMIM][PF(6)], 1-hexyl-3-methylimidazolium hexafluorophosphate, [HMIM][PF(6)], 1-octyl-3-methylimidazolium tetrafluoroborate, [OMIM][BF(4)] and water were accurately measured. [BMIM][PF(6)] and [OMIM][BF(4)] were synthesized by adapting a procedure from the literature to a simpler, single-vessel and faster methodology, with a much lesser consumption of organic solvent. We employed the solvation-parameter model to elucidate the general chemical interactions involved in RTIL/water partitioning. With this purpose, we have selected different solute descriptor parameters that measure polarity, polarizability, hydrogen-bond-donor and hydrogen-bond-acceptor interactions, and cavity formation for a set of specifically selected probe molecules (the training set). The obtained multiparametric equations were used to predict the partition coefficients for compounds not present in the training set (the test set), most being of biological interest. Partial solubility of the ionic liquid in water (and water into the ionic liquid) was taken into account to explain the obtained results. This fact has not been deeply considered up to date. Solute descriptors were obtained from the literature, when available, or else calculated through commercial software. An excellent agreement between calculated and experimental log P(IL/w) values was obtained, which demonstrated that the resulting multiparametric equations are robust and allow predicting partitioning for any organic molecule in the biphasic systems studied.

Compounds and methods for the production of long chain hydrocarbons from biological sources

DOEpatents

Gordon, John Cameron; Silks, Louis A; Sutton, Andrew D; Wu, Ruilian; Schlaf, Marcel; Waldie, Fraser; West, Ryan; Collias, Dimitris Ioannis

2016-08-23

The present invention is directed to the preparation of oxygenated, unsaturated hydrocarbon compounds, such as derivatives of furfural or hydroxymethyl furfural produced by aldol condensation with a ketone or a ketoester, as well as methods of deoxidatively reducing those compounds with hydrogen under acidic conditions to provide saturated hydrocarbons useful as fuels.

Catalytic Dehydrogenative Coupling of Hydrosilanes with Alcohols for the Production of Hydrogen On-demand: Application of a Silane/Alcohol Pair as a Liquid Organic Hydrogen Carrier.

PubMed

Ventura-Espinosa, David; Carretero-Cerdán, Alba; Baya, Miguel; García, Hermenegildo; Mata, Jose A

2017-08-10

The compound [Ru(p-cym)(Cl) 2 (NHC)] is an effective catalyst for the room-temperature coupling of silanes and alcohols with the concomitant formation of molecular hydrogen. High catalyst activity is observed for a variety of substrates affording quantitative yields in minutes at room temperature and with a catalyst loading as low as 0.1 mol %. The coupling reaction is thermodynamically and, in the presence of a Ru complex, kinetically favourable and allows rapid molecular hydrogen generation on-demand at room temperature, under air, and without any additive. The pair silane/alcohol is a potential liquid organic hydrogen carrier (LOHC) for energy storage over long periods in a safe and secure way. Silanes and alcohols are non-toxic compounds and do not require special handling precautions such as high pressure or an inert atmosphere. These properties enhance the practical applications of the pair silane/alcohol as a good LOHC in the automotive industry. The variety and availability of silanes and alcohols permits a pair combination that fulfils the requirements for developing an efficient LOHC. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Redetermination of piperidinium hydrogen sulfide structure

NASA Technical Reports Server (NTRS)

Andras, Maria T.; Hepp, Aloysius F.; Fanwick, Phillip E.; Duraj, Stan A.; Gordon, Edward M.

1994-01-01

The presence of adventitious water in a reaction between dicyclopentamethylene thiuram-disulfide (C5H10NCS2)(sub 2) and a picoline solution of tricyclopentadienyl indium(III) (C5H5)(sub 3). It resulted in the formation of piperidinium hydrogen sulfide (C5H13NS). The piperidinium hydrogen sulfide produced in this way was unambiguously characterized by X-ray crystallography. The structure determination showed that the piperidinium hydrogen sulfide crystal (MW = 119.23 g/mol) has an orthorhombic (Pbcm) unit cell whose parameters are: a = 9.818(2), b = 7.3720(1), c = 9.754(1) A, V = 706.0(3) A(exp 3), Z=4. D(sub chi) = 1.122 g cm(exp -3), Mo K(alpha) (lamda = 0.71073), mu= 3.36 cm(exp -1), F(000) = 264.0, T =293 K, R = 0.036 for 343 reflections with F(sub O)(sup 2) greater than 3 sigma (F(sub O)(sup 2)) and 65 variables. The compound consists of (C5H10NH2)(+) cations and (SH)(-) anions with both species residing on crystallographic mirror planes. N-H -- S hydrogen bonding contributes to the interconnection of neighboring piperidinium components of the compound.

Comprehensive physicochemical studies of a new hybrid material: 2-amino-4-methyl-3-nitropyridinium hydrogen oxalate.

PubMed

Bryndal, I; Kucharska, E; Wandas, M; Lorenc, J; Hermanowicz, K; Mączka, M; Lis, T; Marchewka, M; Hanuza, J

2014-01-03

A new organic-organic salt, 2-amino-4-methyl-3-nitropyridinium hydrogen oxalate (AMNPO), and its deuterium analogue have been synthesized and characterized by means of FT-IR, FT-Raman, DSC and single crystal X-ray studies. The DSC measurements and temperature dependence of the IR and Raman spectra in the range 4-295 K show that it undergoes a reversible phase transition at ~240 K. At room temperature it crystallizes in noncentrosymmetric space group P21. The unit-cell is built of the 2-amino-4-methyl-3-nitropyridinium cations and oxalate monoanions which are connected via the N-H···O and O-H···O hydrogen bonds. The geometrical and hydrogen bond parameters are similar for non-deuterated (at 120 and 293 K) and deuterated compounds (at 90K). The phase transition is probably a consequence of order-disorder transition inside of hydrogen network. The 6-311G(2d,2p) basis set with B3LYP functional have been used to discuss the structure and vibrational spectra of the studied compound. Copyright © 2013 Elsevier B.V. All rights reserved.

Hydrogen bonding pattern in N-benzoyl(- DL-)- L-phenylalanines as revealed by solid-state NMR spectroscopy

NASA Astrophysics Data System (ADS)

Potrzebowski, M. J.; Schneider, C.; Tekely, P.

1999-11-01

The nature of the hydrogen bonding pattern has been investigated in N-benzoyl- DL-phenylalanine ( 1) and N-benzoyl- L-phenylalanine ( 2) polymorphes by solid-state NMR spectroscopy. It has been shown that the multiple resonances of carboxyl carbon in 2 are directly connected to different types of hydrogen bonding. The differences in intermolecular distances of carboxyl groups involved in different types of hydrogen bonding have been visualized by the 2D exchange and 1D ODESSA experiments. Potential applications of such a new approach include the exploration of intermolecular distances in hydrogen bonded compounds with singly labeled biomolecules.

Methods for improved growth of group III nitride semiconductor compounds

DOEpatents

Melnik, Yuriy; Chen, Lu; Kojiri, Hidehiro

2015-03-17

Methods are disclosed for growing group III-nitride semiconductor compounds with advanced buffer layer technique. In an embodiment, a method includes providing a suitable substrate in a processing chamber of a hydride vapor phase epitaxy processing system. The method includes forming an AlN buffer layer by flowing an ammonia gas into a growth zone of the processing chamber, flowing an aluminum halide containing precursor to the growth zone and at the same time flowing additional hydrogen halide or halogen gas into the growth zone of the processing chamber. The additional hydrogen halide or halogen gas that is flowed into the growth zone during buffer layer deposition suppresses homogeneous AlN particle formation. The hydrogen halide or halogen gas may continue flowing for a time period while the flow of the aluminum halide containing precursor is turned off.

Hydrides of intermetallic compounds with a H/M ratio greater than unity obtained at high hydrogen pressures

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

Semenenko, K.N.; Klyamkin, S.N.

1993-11-01

Novel hydride phases with H/M > 1 based on Zr{sub 2}Pd, Hf{sub 2}Pd, and Hf{sub 2}Cu (structures of the MoSi{sub 2} type) have been synthesized at high H{sub 2} pressures. The X-ray diffraction investigations of the resulting hydrides have been carried out. Some factors determining the maximum hydrogen content in the hydrides of intermetallic compounds are discussed. A model structure of the hydrides obtained is proposed, which assumes the possibility of direct H-H interactions when the interatomic distances are less than 1 {angstrom}.

Characterization of toluene and ethylbenzene biodegradation under nitrate-, iron(III)- and manganese(IV)-reducing conditions by compound-specific isotope analysis.

PubMed

Dorer, Conrad; Vogt, Carsten; Neu, Thomas R; Stryhanyuk, Hryhoriy; Richnow, Hans-Hermann

2016-04-01

Ethylbenzene and toluene degradation under nitrate-, Mn(IV)-, or Fe(III)-reducing conditions was investigated by compound specific stable isotope analysis (CSIA) using three model cultures (Aromatoleum aromaticum EbN1, Georgfuchsia toluolica G5G6, and a Azoarcus-dominated mixed culture). Systematically lower isotope enrichment factors for carbon and hydrogen were observed for particulate Mn(IV). The increasing diffusion distances of toluene or ethylbenzene to the solid Mn(IV) most likely caused limited bioavailability and hence resulted in the observed masking effect. The data suggests further ethylbenzene hydroxylation by ethylbenzene dehydrogenase (EBDH) and toluene activation by benzylsuccinate synthase (BSS) as initial activation steps. Notably, significantly different values in dual isotope analysis were detected for toluene degradation by G. toluolica under the three studied redox conditions, suggesting variations in the enzymatic transition state depending on the available TEA. The results indicate that two-dimensional CSIA has significant potential to assess anaerobic biodegradation of ethylbenzene and toluene at contaminated sites. Copyright © 2015 Elsevier Ltd. All rights reserved.

Use of the Analysis of the Volatile Faecal Metabolome in Screening for Colorectal Cancer

PubMed Central

2015-01-01

Diagnosis of colorectal cancer is an invasive and expensive colonoscopy, which is usually carried out after a positive screening test. Unfortunately, existing screening tests lack specificity and sensitivity, hence many unnecessary colonoscopies are performed. Here we report on a potential new screening test for colorectal cancer based on the analysis of volatile organic compounds (VOCs) in the headspace of faecal samples. Faecal samples were obtained from subjects who had a positive faecal occult blood sample (FOBT). Subjects subsequently had colonoscopies performed to classify them into low risk (non-cancer) and high risk (colorectal cancer) groups. Volatile organic compounds were analysed by selected ion flow tube mass spectrometry (SIFT-MS) and then data were analysed using both univariate and multivariate statistical methods. Ions most likely from hydrogen sulphide, dimethyl sulphide and dimethyl disulphide are statistically significantly higher in samples from high risk rather than low risk subjects. Results using multivariate methods show that the test gives a correct classification of 75% with 78% specificity and 72% sensitivity on FOBT positive samples, offering a potentially effective alternative to FOBT. PMID:26086914

FIELD STUDY: IN SITU OXIDATION OF 1,4-DIOXANE WITH OZONE AND HYDROGEN PEROXIDE

EPA Science Inventory

A pilot-scale field evaluation is underway to assess the effectiveness of in situ oxidation (using ozone with and without hydrogen peroxide) for remediation of 1,4-dioxane and chlorinated volatile organic compounds in groundwater at the Cooper Drum Company Superfund Site located ...

(E)-2-(2-Methyl­cyclo­hexyl­idene)hydrazinecarbothio­amide

PubMed Central

Hicks, Justin W.; Lough, Alan J.; Wilson, Alan A.; Vasdev, Neil

2011-01-01

In the crystal of the title compound, C8H15N3S, mol­ecules are linked by N—H⋯S hydrogen bonds, forming chains along [10]. An intra­molecular N—H⋯N hydrogen bond is also present. PMID:22220022

Safety in the Chemical Laboratory. Chemical Laboratory Safety: The Academic Anomaly.

ERIC Educational Resources Information Center

Bretherick, Leslie

1990-01-01

Discussed are accidents that occur in the laboratories of highly trained chemists. Four examples are provided to illustrate potential hazards that are often overlooked in chemistry laboratories, molten inorganic salt baths, the reaction of acetone and hydrogen peroxide, halogenated acetylene compounds, and the reaction of hydrogen peroxide and…

40 CFR 60.2875 - What definitions must I know?

Code of Federal Regulations, 2013 CFR

2013-07-01

... purified carbon monoxide that is used as an intermediate in the production of other chemical compounds. (6) Units burning only hydrocarbon liquids or solids to produce hydrogen, carbon monoxide, synthesis gas, or... hydrogen, carbon monoxide, synthesis gas, or other gases for use in other manufacturing processes. (7...

40 CFR 60.2875 - What definitions must I know?

Code of Federal Regulations, 2014 CFR

2014-07-01

... purified carbon monoxide that is used as an intermediate in the production of other chemical compounds. (6) Units burning only hydrocarbon liquids or solids to produce hydrogen, carbon monoxide, synthesis gas, or... hydrogen, carbon monoxide, synthesis gas, or other gases for use in other manufacturing processes. (7...

FIXED-BED HYDROGENATION OF ORGANIC COMPOUNDS IN SUPERCRITICAL CARBON DIOXIDE. (R826034)

EPA Science Inventory

Abstract

The Pd/C hydrogenation of cyclohexene to cyclohexane was performed in a continuous fixed-bed reactor employing CO₂ to solubilize the reaction mixture in a single supercritical (sc) phase surrounding the solid catalyst. Employing an equimolar feed of...

Revisiting the Meerwein-Ponndorf-Verley Reduction: A Sustainable Protocol for Transfer Hydrogenation of Aldehydes and Ketones

EPA Science Inventory

The metal-catalyzed transfer hydrogenation of carbonyl compounds has received much interest because of the immense number of opportunities that exist to prepare high-value products. This reaction is featured in numerous multi-step organic syntheses and is arguably the most import...

Thermal expansion of L-ascorbic acid

NASA Astrophysics Data System (ADS)

Nicolaï, B.; Barrio, M.; Tamarit, J.-Ll.; Céolin, R.; Rietveld, I. B.

2017-04-01

The specific volume of vitamin C has been investigated by X-ray powder diffraction as a function of temperature from 110 K up to complete degradation around 440 K. Its thermal expansion is relatively small in comparison with other organic compounds with an expansivity α v of 1.2(3) × 10-4 K-1. The structure consists of strongly bound molecules in the ac plane through a dense network of hydrogen bonds. The thermal expansion is anisotropic. Along the b axis, the expansion has most leeway and is about 10 times larger than in the other directions.

Factors affecting activated carbon-based catalysts for selective hydrogen sulfide oxidation

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

Li, Huixing; Monnell, J.D.; Alvin, M.A.

2008-09-01

The primary product of coal gasification processes is synthesis gas (syngas), a mixture of CO, H2, CO2, H2O and a number of minor components. Among the most significant minor components in syngas is hydrogen sulfide (H2S). In addition to its adverse environmental impact, H2S poisons the catalysts and hydrogen purification membranes, and causes severe corrosion in gas turbines. Technologies that can remove H2S from syngas and related process streams are, therefore, of considerable practical interest. To meet this need, we work towards understanding the mechanism by which prospective H2S catalysts perform in simulated fuel gas conditions. Specifically, we show thatmore » for low-temperature gas clean-up (~1408C) using activated carbon fibers and water plays a significant role in H2S binding and helps to prolong the lifetime of the material. Basic surface functional groups were found to be imperative for significant conversion of H2S to daughter compounds, whereas metal oxides (La and Ce) did little to enhance this catalysis. We show that although thermal regeneration of the material is possible, the regenerated material has a substantially lower catalytic and sorption capacity.« less

Advanced water splitting for green hydrogen gas production through complete oxidation of starch by in vitro metabolic engineering.

PubMed

Kim, Jae-Eung; Kim, Eui-Jin; Chen, Hui; Wu, Chang-Hao; Adams, Michael W W; Zhang, Y-H Percival

2017-11-01

Starch is a natural energy storage compound and is hypothesized to be a high-energy density chemical compound or solar fuel. In contrast to industrial hydrolysis of starch to glucose, an alternative ATP-free phosphorylation of starch was designed to generate cost-effective glucose 6-phosphate by using five thermophilic enzymes (i.e., isoamylase, alpha-glucan phosphorylase, 4-α-glucanotransferase, phosphoglucomutase, and polyphosphate glucokinase). This enzymatic phosphorolysis is energetically advantageous because the energy of α-1,4-glycosidic bonds among anhydroglucose units is conserved in the form of phosphorylated glucose. Furthermore, we demonstrated an in vitro 17-thermophilic enzyme pathway that can convert all glucose units of starch, regardless of branched and linear contents, with water to hydrogen at a theoretic yield (i.e., 12 H 2 per glucose), three times of the theoretical yield from dark microbial fermentation. The use of a biomimetic electron transport chain enabled to achieve a maximum volumetric productivity of 90.2mmol of H 2 /L/h at 20g/L starch. The complete oxidation of starch to hydrogen by this in vitro synthetic (enzymatic) biosystem suggests that starch as a natural solar fuel becomes a high-density hydrogen storage compound with a gravimetric density of more than 14% H 2 -based mass and an electricity density of more than 3000Wh/kg of starch. Copyright © 2017. Published by Elsevier Inc.

Situ treatment of contaminated groundwater

DOEpatents

McNab, Jr., Walt W.; Ruiz, Roberto; Pico, Tristan M.

2001-01-01

A system for treating dissolved halogenated organic compounds in groundwater that relies upon electrolytically-generated hydrogen to chemically reduce the halogenated compounds in the presence of a suitable catalyst. A direct current is placed across at least a pair, or an array, of electrodes which are housed within groundwater wells so that hydrogen is generated at the cathode and oxygen at the anode. A pump is located within the well housing in which the cathode(s) is(are) located and draws in groundwater where it is hydrogenated via electrolysis, passes through a well-bore treatment unit, and then transported to the anode well(s) for reinjection into the ground. The well-bore treatment involves a permeable cylinder located in the well bore and containing a packed bed of catalyst material that facilitates the reductive dehalogenation of the halogenated organic compounds by hydrogen into environmentally benign species such as ethane and methane. Also, electro-osmatic transport of contaminants toward the cathode also contributes to contaminant mass removal. The only above ground equipment required are the transfer pipes and a direct circuit power supply for the electrodes. The electrode wells in an array may be used in pairs or one anode well may be used with a plurality of cathode wells. The DC current flow between electrode wells may be periodically reversed which controls the formation of mineral deposits in the alkaline cathode well-bore water, as well as to help rejuvenate the catalysis.

Hydrogen storage in lithium hydride: A theoretical approach

NASA Astrophysics Data System (ADS)

Banger, Suman; Nayak, Vikas; Verma, U. P.

2018-04-01

First principles calculations have been carried out to analyze structural stability of lithium hydride (LiH) in NaCl phase using the full potential linearized augmented plane wave (FP-LAPW) method within the framework of density functional theory (DFT). Calculations have been extended to physiosorbed H-atom compounds LiH·H2, LiH·3H2 and LiH·4H2. The obtained results are discussed in the paper. The results for LiH are in excellent agreement with earlier reported data. The obtained direct energy band gap of LiH is 3.0 eV which is in excellent agreement with earlier reported theoretical band gap. The electronic band structure plots of the hydrogen adsorbed compounds show metallic behavior. The elastic constants, anisotropy factor, shear modulus, Young's modulus, Poisson's ratio and cohesive energies of all the compounds are calculated. Calculation of the optical spectra such as the real and imaginary parts of dielectric function, optical reflectivity, absorption coefficient, optical conductivity, refractive index, extinction coefficient and electron energy loss are performed for the energy range 0-15 eV. The obtained results for LiH·H2, LiH·3H2 and LiH·4H2, are reported for the first time. This study has been made in search of materials for hydrogen storage. It is concluded that LiH is a promising material for hydrogen storage.

Halogenated Organic Compounds Identified in Hydraulic Fracturing Wastewaters Using Ultrahigh Resolution Mass Spectrometry.

PubMed

Luek, Jenna L; Schmitt-Kopplin, Philippe; Mouser, Paula J; Petty, William Tyler; Richardson, Susan D; Gonsior, Michael

2017-05-16

Large volumes of water return to the surface following hydraulic fracturing of deep shale formations to retrieve oil and natural gas. Current understanding of the specific organic constituents in these hydraulic fracturing wastewaters is limited to hydrocarbons and a fraction of known chemical additives. In this study, we analyzed hydraulic fracturing wastewater samples using ultrahigh resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) as a nontargeted technique to assign unambiguous molecular formulas to singly charged molecular ions. Halogenated molecular formulas were identified and confirmed using isotopic simulation and MS-MS fragmentation spectra. The abundance of halogenated organic compounds in flowback fluids rather than older wastewaters suggested that the observed molecular ions might have been related to hydraulic fracturing additives and related subsurface reactions, such as through the reaction of shale-extracted chloride, bromide, and iodide with strong oxidant additives (e.g., hypochlorite, persulfate, hydrogen peroxide) and subsequently with diverse dissolved organic matter. Some molecular ions matched the exact masses of known disinfection byproducts including diiodoacetic acid, dibromobenzoic acid, and diiodobenzoic acid. The identified halogenated organic compounds, particularly iodinated organic molecules, are absent from inland natural systems and these compounds could therefore play an important role as environmental tracers.

Perspective on recent developments on sulfur-containing agents and hydrogen sulfide signaling.

PubMed

Jacob, Claus; Anwar, Awais; Burkholz, Torsten

2008-10-01

The last couple of years have witnessed the coming together of several initially unconnected lines of investigation which now link natural sulfur products to hydrogen sulfide release and wide ranging cardiovascular protection. It has become apparent that sulfur compounds contained within garlic, onions, mushrooms and various edible beans and fruits may be transformed chemically or enzymatically in the human body with subsequent formation of hydrogen sulfide. The latter has emerged during the last decade from a shadowy existence as toxic gas to be recognized as the third gaseous transmitter besides nitric oxide ( (.)NO) and carbon monoxide (CO). Hydrogen sulfide is formed endogenously in the human body by enzymes such as cystathionine beta-synthase (CBS) in the brain and cystathionine gamma-lyase (CSE) in liver, vascular and non-vascular smooth muscle. Although its exact chemical and biochemical modes of action are still not fully understood, levels of hydrogen sulfide in the brain and vasculature have unambiguously been associated with human health and disease. Not surprisingly, agents releasing hydrogen sulfide, as well as inhibitors of hydrogen sulfide synthesis (CBS and CSE inhibitors) have been investigated. Apart from linking our daily diet to a healthy brain and cardiovasculature, these findings may also provide new leads for drug design. Future studies will therefore need to focus on how such compounds are formed and transformed in the relevant plants, how food processing affects their chemical constitution, and how they release hydrogen sulfide (or control its levels) in the human body. Such multidisciplinary research should ultimately answer the all-important question if a hearty diet is also good for the heart.

Spectroscopic, DFT, and XRD Studies of Hydrogen Bonds in N-Unsubstituted 2-Aminobenzamides.

PubMed

Mphahlele, Malose Jack; Maluleka, Marole Maria; Rhyman, Lydia; Ramasami, Ponnadurai; Mampa, Richard Mokome

2017-01-04

The structures of the mono- and the dihalogenated N -unsubstituted 2-aminobenzamides were characterized by means of the spectroscopic (¹H-NMR, UV-Vis, FT-IR, and FT-Raman) and X-ray crystallographic techniques complemented with a density functional theory (DFT) method. The hindered rotation of the C(O)-NH₂ single bond resulted in non-equivalence of the amide protons and therefore two distinct resonances of different chemical shift values in the ¹H-NMR spectra of these compounds were observed. 2-Amino-5-bromobenzamide ( ABB ) as a model confirmed the presence of strong intramolecular hydrogen bonds between oxygen and the amine hydrogen. However, intramolecular hydrogen bonding between the carbonyl oxygen and the amine protons was not observed in the solution phase due to a rapid exchange of these two protons with the solvent and fast rotation of the Ar-NH₂ single bond. XRD also revealed the ability of the amide unit of these compounds to function as a hydrogen bond donor and acceptor simultaneously to form strong intermolecular hydrogen bonding between oxygen of one molecule and the NH moiety of the amine or amide group of the other molecule and between the amine nitrogen and the amide hydrogen of different molecules. DFT calculations using the B3LYP/6-311++G(d,p) basis set revealed that the conformer ( A ) with oxygen and 2-amine on the same side predominates possibly due to the formation of a six-membered intramolecular ring, which is assisted by hydrogen bonding as observed in the single crystal XRD structure.

Isotope Tales: Remaining Problems, Unsolvable Questions, and Gentle Successes

NASA Astrophysics Data System (ADS)

fogel, marilyn; bradley, christina; newsome, seth; filipp, fabian

2014-05-01

Earth's biomes function and adapt today as climate changes and ecosystems and the organisms within them adapt. Stable isotope biogeochemistry has had a major influence in understanding climate perturbations and continues to be an active area of research on many fronts. Banking on the success of compound specific stable isotope analyses of amino acids, nitrogen, carbon, and hydrogen isotopes continue to reveal subtle shifts in oceanic food webs and metabolic changes in microbes, plants, and animals. A biochemical understanding of exactly how organisms process and partition stable isotopes during metabolism remains unsolved, but is required if this field is to move beyond description to quantitation. Although the patterns of carbon and nitrogen isotopes are fairly well established in the common amino acids, we need to consider specifics: How do shifting metabolic pathways (metabolomics) influence the outcome of stable isotope partitioning? What influence does the gut microflora in animals have on isotopic labeling? What are the intramolecular isotope patterns of common amino acids and what do they tell us? What can be learned with other isotope systems, such as hydrogen? Results and ideas of how to move forward in this field will be presented starting at the molecular level and ending with ecosystems.

Optimization and application of atmospheric pressure chemical and photoionization hydrogen-deuterium exchange mass spectrometry for speciation of oxygen-containing compounds.

PubMed

Acter, Thamina; Kim, Donghwi; Ahmed, Arif; Jin, Jang Mi; Yim, Un Hyuk; Shim, Won Joon; Kim, Young Hwan; Kim, Sunghwan

2016-05-01

This paper presents a detailed investigation of the feasibility of optimized positive and negative atmospheric pressure chemical ionization (APCI) mass spectrometry (MS) and atmospheric pressure photoionization (APPI) MS coupled to hydrogen-deuterium exchange (HDX) for structural assignment of diverse oxygen-containing compounds. The important parameters for optimization of HDX MS were characterized. The optimized techniques employed in the positive and negative modes showed satisfactory HDX product ions for the model compounds when dichloromethane and toluene were employed as a co-solvent in APCI- and APPI-HDX, respectively. The evaluation of the mass spectra obtained from 38 oxygen-containing compounds demonstrated that the extent of the HDX of the ions was structure-dependent. The combination of information provided by different ionization techniques could be used for better speciation of oxygen-containing compounds. For example, (+) APPI-HDX is sensitive to compounds with alcohol, ketone, or aldehyde substituents, while (-) APPI-HDX is sensitive to compounds with carboxylic functional groups. In addition, the compounds with alcohol can be distinguished from other compounds by the presence of exchanged peaks. The combined information was applied to study chemical compositions of degraded oils. The HDX pattern, double bond equivalent (DBE) distribution, and previously reported oxidation products were combined to predict structures of the compounds produced from oxidation of oil. Overall, this study shows that APCI- and APPI-HDX MS are useful experimental techniques that can be applied for the structural analysis of oxygen-containing compounds.

Catalytic hydrogenation using complexes of base metals with tridentate ligands

DOEpatents

Hanson, Susan K.; Zhang, Guoqi; Vasudevan, Kalyan V.

2017-02-14

Complexes of cobalt and nickel with tridentate ligand PNHP.sup.R are effective for hydrogenation of unsaturated compounds. Cobalt complex [(PNHP.sup.Cy)Co(CH.sub.2SiMe.sub.3)]BAr.sup.F.sub.4 (PNHP.sup.Cy=bis[2-(dicyclohexylphosphino)ethyl]amine, BAr.sup.F.sub.4=B(3,5-(CF.sub.3).sub.2C.sub.6H.sub.3).sub.4)) was prepared and used with hydrogen for hydrogenation of alkenes, aldehydes, ketones, and imines under mild conditions (25-60.degree. C., 1-4 atm H.sub.2). Nickel complex [(PNHP.sup.Cy)Ni(H)]BPh.sub.4 was used for hydrogenation of styrene and 1-octene under mild conditions. (PNP.sup.Cy)Ni(H) was used for hydrogenating alkenes.

Catalytic hydrogenation using complexes of base metals with tridentate ligands

DOEpatents

Vasudevan, Kalyan V.; Zhang, Guoqi; Hanson, Susan K.

2016-09-06

Complexes of cobalt and nickel with tridentate ligand PNHP.sup.R are effective for hydrogenation of unsaturated compounds. Cobalt complex [(PNHP.sup.Cy)Co(CH.sub.2SiMe.sub.3)]BAr.sup.F.sub.4 (PNHP.sup.Cy=bis[2-(dicyclohexylphosphino)ethyl]amine, BAr.sup.F.sub.4=B(3,5-(CF.sub.3).sub.2C.sub.6H.sub.3).sub.4)) was prepared and used with hydrogen for hydrogenation of alkenes, aldehydes, ketones, and imines under mild conditions (25-60.degree. C., 1-4 atm H.sub.2). Nickel complex [(PNHP.sup.Cy)Ni(H)]BPh.sub.4 was used for hydrogenation of styrene and 1-octene under mild conditions. (PNP.sup.Cy)Ni(H) was used for hydrogenating alkenes.

Late-Transition-Metal-Modified β-Mo 2C Catalysts for Enhanced Hydrogenation during Guaiacol Deoxygenation

DOE PAGES

Baddour, Frederick G.; Witte, Vanessa A.; Nash, Connor P.; ...

2017-10-26

Molybdenum carbide has been identified as a promising bifunctional catalyst in the deoxygenation of a variety of pyrolysis vapor model compounds. Although high deoxygenation activity has been demonstrated, complementary hydrogenation activity has been limited, especially for lignin-derived, aromatic model compounds. The ability to control the relative site densities of acidic and hydrogenation functionalities represents a catalyst design challenge for these materials with the goal to improve hydrogenation activity under ex situ catalytic fast pyrolysis (CFP) conditions. Here in this paper, we demonstrate that the addition of Pt and Ni to Mo 2C resulted in an increase in the H*-site densitymore » with only a minor decrease in the acid-site density. In contrast, the addition of Pd did not significantly alter the H* or acid site densities. High conversions (>94%) and high selectivities to 0-oxygen products (>80%) were observed in guaiacol deoxygenation under ex situ CFP conditions (350 °C and 0.44 MPa H 2) for all catalysts. Pt addition resulted in the greatest deoxygenation, and site-time yields to hydrogenated products over the Pt/Mo 2C catalyst were increased to 0.048 s -1 compared to 0.015-0.019 s -1 for all other catalysts. The Pt/Mo 2C catalyst demonstrated the highest hydrogenation performance, but modification with Ni also significantly enhanced hydrogenation performance, representing a promising lower-cost alternative.« less

Hydrogen-transfer and charge-transfer in photochemical and radiation induced reactions. Progress report, November 1, 1975--October 31, 1976

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

Cohen, S.G.

The relative importance of light absorption, quenching of triplet, and hydrogen transfer repair has been examined in retardation by mercaptans of photoreduction of aromatic ketones by alcohols. In the reduction of benzophenone by 2-propanol, retardation is efficient and, after correction for the first two effects, is due entirely to hydrogen-transfer repair, as indicated by deuterium labeling. In reduction of acetophenone by ..cap alpha..-methylbenzyl alcohol, repair by hydrogen transfer is also operative. In reduction of benzophenone by benzhydrol, retardation is less efficient and is due to quenching, as the ketyl radical does not abstract hydrogen from mercaptan rapidly in competition withmore » coupling. Deuterium isotope effects are discussed in terms of competitive reactions. Photoreduction of benzophenone by 2-butylamine and by triethylamine is retarded by aromatic mercaptans and disulfides. Of the retardation not due to light absorption and triplet quenching by the sulfur compounds, half is due to hydrogen-transfer repair, as indicated by racemization and deuterium labeling. The remainder is attributed to quenching by the sulfur compound of the charge-transfer-complex intermediate. Photoreduction by primary and secondary amines, but not by tertiary amines, is accelerated by aliphatic mercaptans. The acceleration is attributed to catalysis of hydrogen transfer by the mercaptan in the charge-transfer complex. The effect is large in hydrocarbon solvent, less in polar organic solvents and absent in water.« less

Late-Transition-Metal-Modified β-Mo 2C Catalysts for Enhanced Hydrogenation during Guaiacol Deoxygenation

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

Baddour, Frederick G.; Witte, Vanessa A.; Nash, Connor P.

Molybdenum carbide has been identified as a promising bifunctional catalyst in the deoxygenation of a variety of pyrolysis vapor model compounds. Although high deoxygenation activity has been demonstrated, complementary hydrogenation activity has been limited, especially for lignin-derived, aromatic model compounds. The ability to control the relative site densities of acidic and hydrogenation functionalities represents a catalyst design challenge for these materials with the goal to improve hydrogenation activity under ex situ catalytic fast pyrolysis (CFP) conditions. Here in this paper, we demonstrate that the addition of Pt and Ni to Mo 2C resulted in an increase in the H*-site densitymore » with only a minor decrease in the acid-site density. In contrast, the addition of Pd did not significantly alter the H* or acid site densities. High conversions (>94%) and high selectivities to 0-oxygen products (>80%) were observed in guaiacol deoxygenation under ex situ CFP conditions (350 °C and 0.44 MPa H 2) for all catalysts. Pt addition resulted in the greatest deoxygenation, and site-time yields to hydrogenated products over the Pt/Mo 2C catalyst were increased to 0.048 s -1 compared to 0.015-0.019 s -1 for all other catalysts. The Pt/Mo 2C catalyst demonstrated the highest hydrogenation performance, but modification with Ni also significantly enhanced hydrogenation performance, representing a promising lower-cost alternative.« less

New 7-arylpiperazinylalkyl-8-morpholin-4-yl-purine-2,6-dione derivatives with anxiolytic activity - Synthesis, crystal structure and structure-activity study

NASA Astrophysics Data System (ADS)

Chłoń-Rzepa, Grażyna; Żmudzki, Paweł; Pawłowski, Maciej; Wesołowska, Anna; Satała, Grzegorz; Bojarski, Andrzej J.; Jabłoński, Mateusz; Kalinowska-Tłuścik, Justyna

2014-06-01

On the basis of our earlier studies with serotonin (5-HT) receptor ligands in the group of long-chain arylpiperazines (LCAPs), a new series of 7-arylpiperazinylalkyl-8-morpholin-4-yl-purine-2,6-dione derivatives (5-12) has been designed, synthesised and studied in vitro for their affinity for 5-HT1A, 5-HT2A, 5-HT6 and 5-HT7 receptors. The introduction of o-OCH3 and m-Cl into the phenylpiperazinyl moiety as well as the elongation of the linker between purine-2,6-dione core and arylpiperazine fragment modified the affinity for the tested 5-HT receptors. The structures of compounds 9-11 (hydrochloride salts) were confirmed by an X-ray diffraction method. All molecules adopted a different conformation in the crystal. The strongest observed type of interaction is a charge assisted hydrogen bond N+-H⋯Cl-. Additionally, the π-π interactions between 1,3-dimethyl-3,7-dihydropurine-2,6-dione cores of the neighbouring molecules were also observed. As it is observed in the presented crystal structures, the morpholine ring (a potential donor and acceptor of the hydrogen bonds) seems to be an attractive substituent, that may support binding to the non-specific sites of 5-HT receptors. Another interesting feature is the mutual orientation of rings in the arylpiperazine fragment, with plausible influence on ligand-receptor recognition. For compound 10, with strong 5-HT1A binding affinity, the mutual orientation of rings is determined by the intramolecular weak C-H⋯O hydrogen bond. This observation may contribute to a better understanding of the more selective binding of o-OCH3 arylpiperazine derivatives to the 5-HT1A receptor.

In situ bioremediation of petroleum hydrocarbons and chlorinated hydrocarbons: Three case studies

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

Bost, R.C.; Perry, R.G.; Barber, T.

1997-06-01

In situ biodegradation of organic contaminants is one of the most cost-effective means of site remediation. This method has proven successful in soils, ground water, and slurries. Bacteria capable of degrading organic contaminants within an aquifer include many species from a wide spectrum of genera, e.g. Pseudomonas, Corynebacterium, Bacillus, etc. In most cases, a mixture of bacterial strains is required to completely oxidize a complex organic contaminant. Each strain of an organism may target a specific compound, working together with other organisms to ultimately degrade each intermediate until complete degradation, also known as mineralization, occurs. One or more of themore » following mechanisms are utilized by bacteria for organic chemical degradation: (1) aerobic, (2) anaerobic, and (3) co-metabolic. During aerobic oxidation of organic chemicals, bacteria utilize the pollutant as an electron and hydrogen source and oxygen acts as the electron and hydrogen acceptor, resulting in water. As the bacterial enzymes cleave the compound, oxidized products are produced along with energy for the reaction to proceed. This is the most rapid and widely utilized mechanism. Dehalogenation occurs under aerobic, or perhaps more often, under anoxic conditions. This process occurs in the presence of alternate electron acceptors and replaces chlorine with hydrogen. The mechanism of co-metabolism can be aerobic or anaerobic, but is more often aerobic. This process requires a separate energy source for the bacterial cell because the pollutant is not utilized as an energy source. The role of bioremediation in site remediation is demonstrated below by three case studies: (1) a refinery, (2) a municipal landfill and (3) a pesticide formulation plant.« less

Hydrodeoxygenation of coal using organometallic catalyst precursors

NASA Astrophysics Data System (ADS)

Kirby, Stephen R.

2002-04-01

The objective of this dissertation was to determine the desirability of organometallic compounds for the hydrodeoxygenation (HDO) of coal during liquefaction. The primary focus of this study was the removal of phenol-like compounds from coal liquids for the production of a thermally stable jet fuel. Investigation of the HDO ability of an organometallic compound containing both cobalt and molybdenum (CoMo-T2) was achieved using a combination of model compound and coal experiments. Model compounds were chosen representing four oxygen functional groups present in a range of coals. Electron density and bond order calculations were performed for anthrone, dinaphthyl ether, xanthene, di-t-butylmethylphenol, and some of their derivatives to ascertain a potential order of hydrogenolysis and hydrogenation reactivity for these compounds. The four model compounds were then reacted with CoMo-T2, as well as ammonium tetrathiomolybdate (ATTM). Products of reaction were grouped as compounds that had undergone deoxygenation, those that had aromatic rings reduced, those that were products of both reaction pathways, and those produced through other routes. ATTM had an affinity for both reaction types. Its reaction order for the four model compounds with respect to deoxygenated compounds was the same as that estimated from electron density calculations for hydrogenolysis reactivity. CoMo-T2 appeared to show a preference toward hydrogenation, although deoxygenated products were still achieved in similar, or greater, yields, for almost all the model compounds. The reactivity order achieved for the four compounds with CoMo-T2 was similar to that estimated from bond order calculations for hydrogenation reactivity. Three coals were selected representing a range of coal ranks and oxygen contents. DECS-26 (Wyodak), DECS-24 (Illinois #6), and DECS-23 (Pittsburgh #8) were analyzed by CPMAS 13C NMR and pyrolysis-GC-MS to determine the functional groups comprising the oxygen content of these coals. Trends within the data were similar to those reported by other authors. Based on the conclusions from both the model compound studies and the coal analysis, predictions were made of the catalyst precursors' performance in the HDO of the three selected coals. It was concluded that CoMo-T2 is a desirable catalyst precursor for the HDO of coals (particularly low-rank coals), but that an optimum set of conditions must be determined to take full advantage of its HDO ability. (Abstract shortened by UMI.)

Tantalum-containing catalyst useful for producing alcohols from synthesis gas

DOEpatents

Kinkade, N.E.

1992-04-07

A catalyst is described which is useful for selectively converting a mixture of carbon monoxide and hydrogen to a mixture of lower alkanols. The catalyst consists essentially of a mixture of molybdenum sulfide, an alkali metal compound and a tantalum compound.

Automatic environmental disinfection with hydrogen peroxide and silver ions versus manual environmental disinfection with sodium hypochlorite: a multicentre randomized before-and-after trial.

PubMed

Mosci, D; Marmo, G W; Sciolino, L; Zaccaro, C; Antonellini, R; Accogli, L; Lazzarotto, T; Mongardi, M; Landini, M P

2017-10-01

New technologies for automated disinfection have been developed, including the use of hydrogen peroxide atomized by specific equipment, with associated silver compounds. To compare the effectiveness of an automated disinfection system with hydrogen peroxide <8% and silver ion versus a manual method with 0.5% sodium hypochlorite solution when evaluating the reduction of microbial mesophilic contamination and Clostridium difficile presence; and to evaluate the time required for both of these processes. This was a randomized multicentre trial performed in different hospital wards that had been occupied previously by patients with Clostridium difficile infection. When patients were discharged their rooms were randomized to one of two decontamination arms. The surfaces where sampled using swabs, before and after disinfection. Swab samples were cultured for quantitative detection of microbial mesophilic contamination and qualitative detection of C. difficile. Before disinfection, 13% of surfaces decontaminated with hydrogen peroxide and silver ions and 20% of surfaces decontaminated with sodium hypochlorite showed presence of C. difficile spores. After disinfection, the samples containing C. difficile were 0% (P < 0.001) in the group decontaminated with hydrogen peroxide and silver ions, and were 3% (P < 0.001) in the group decontaminated with sodium hypochlorite. This difference was not statistically significant; nor was the difference in the reduction of the microbial mesophilic contamination. The differences between the groups were not statistically significant; however, the disinfection with hydrogen peroxide and silver ions is preferable due to less dependence on operators. Copyright © 2017 The Healthcare Infection Society. Published by Elsevier Ltd. All rights reserved.

The crystal structures of six (2E)-3-aryl-1-(5-halogeno-thio-phen-2-yl)prop-2-en-1-ones.

PubMed

Naik, Vasant S; Yathirajan, Hemmige S; Jasinski, Jerry P; Smolenski, Victoria A; Glidewell, Christopher

2015-09-01

The structures of six chalcones containing 5-halogeno-thio-phen-2-yl substituents are reported: (2E)-1-(5-chloro-thio-phen-2-yl)-3-(4-ethyl-phen-yl)prop-2-en-1-one, C15H13ClOS, (I), and (2E)-1-(5-bromo-thio-phen-2-yl)-3-(4-ethyl-phen-yl)prop-2-en-1-one, C15H13BrOS, (II), are isostructural in space group P-1, while (2E)-1-(5-chloro-thio-phen-2-yl)-3-(4-eth-oxy-phen-yl)prop-2-en-1-one, C15H13ClO2S, (III), and (2E)-1-(5-bromo-thio-phen-2-yl)-3-(4-eth-oxy-phen-yl)prop-2-en-1-one C15H13BrO2S, (IV), are isostructural in space group P21/c. There are no hydrogen bonds of any kind in the structures of compounds (I) and (II), but in the structures of compounds (III) and (IV), the mol-ecules are linked into C(7) chains by means of C-H⋯O hydrogen bonds. In the structure of (2E)-3-(4-bromo-phen-yl)-1-(5-chloro-thio-phen-2-yl)prop-2-en-1-one, C13H8BrClOS, (V), there are again no hydrogen bonds nor π-π stacking inter-actions but in that of (2E)-1-(5-bromo-thio-phen-2-yl)-3-(3-meth-oxy-phen-yl)prop-2-en-1-one, C14H11BrO2S, (VI), the mol-ecules are linked into C(5) chains by C-H⋯O hydrogen bonds. In each of compounds (I)-(VI), the mol-ecular skeletons are close to planarity, and there are short halogen⋯halogen contacts in the structures of compounds (II) and (V) and a short Br⋯O contact in the structure of compound (VI). Comparisons are made with the structures of some similar compounds.

Continuous catalytic hydrogenation of polyaromatic hydrocarbon compounds in hydrogen-supercritical carbon dioxide.

PubMed

Yuan, Tao; Fournier, Anick R; Proudlock, Raymond; Marshall, William D

2007-03-15

A continuous hydrogenation device was evaluated for the detoxification of selected tri-, tetra-, or pentacyclic polyaromatic hydrocarbon (PAH) compounds {anthracene, phenanthrene, chrysene, and benzo[a]pyrene (B[a]P)} by hydrogenation. A substrate stream in hexane, 0.05-1.0% (w/v), was mixed with hydrogen-carbon dioxide (H2-CO2, 5-30% v/v) and delivered to a heated reactor column (25 cm x 1 cm) containing palladium supported on gamma alumina (Pd0/gamma-Al2O3) that was terminated with a capillary restrictor. The flow rate from the reactor, approximately 800 mL min(-1) decompressed gas, corresponded to 4 mL min(-1) fluid under the operating conditions of the trials. Reaction products were recovered by passing the reactor effluent through hexane. At 90 degrees C, the anthracene or phenanthrene substrate was hydrogenated only partially to octahydro and dodecahydro species and contained only a minor quantity of totally hydrogenated products. For substrates with increasing numbers of fused aromatic rings, the hydrogenation efficiency was decreased further. However, at an increasing temperature (90-150 degrees C) and increasing mobile phase flow rate (20.68 MPa corresponding to 2100 mL min(-1) decompressed gas), B[a]P and chrysene were hydrogenated, virtuallytotally, to their corresponding perhydro analogues (eicosahydrobenzo[a]pyrenes and octadecahydrochrysenes), respectively. That this approach might be useful for decontaminating soil extracts was supported by companion in vitro trials in which the substrate and products were assayed for mutagenic activity with five bacterial strains that are auxotrophic for histidine (Salmonella typhimurium TA98, TA100, TA1535, and TA1537) or tryptophan (Escherichia coliWP2 uvrA), using the bacterial reverse mutation assay (modified Ames test). Generally, substantial increases in revertant colony counts were not observed with any of the strains following exposure to the hydrogenation products in the absence or presence of the 10 or 30% S9 mix, which is consistent with the loss of mutagenic activity from these hydrogenation products.

Bis[2-(hy-droxy-imino-meth-yl)phenolato]nickel(II): a second monoclinic polymorph.

PubMed

Rusanova, Julia A; Buvaylo, Elena A; Rusanov, Eduard B

2011-01-15

The title compound, [Ni(C(7)H(6)NO(2))(2)], (I), is a second monoclinic polymorph of the compound, (II), reported by Srivastava et al. [Acta Cryst. (1967), 22, 922] and Mereiter [Private communication (2002) CCDC refcode NISALO01]. The bond lengths and angles are similar in both structures. The mol-ecule in both structures lies on a crystallographic inversion center and both have an inter-nal hydrogen bond. The title compound crystallizes in the space group P2(1)/c (Z = 2), whereas compound (II) is in the space group P2(1)/n (Z = 2) with a similar cell volume but different cell parameters. In both polymorphs, mol-ecules are arranged in the layers but in contrast to the previously published compound (II) where the dihedral angle between the layers is 86.3°, in the title polymorph the same dihedral angle is 29.4°. The structure of (I) is stabilized by strong intra-molecular O-H⋯O hydrogen bonding between the O-H group and the phenolate O atom.

Edible Oil Barriers for Treatment of Chlorinated Solvent Contaminated Groundwater

DTIC Science & Technology

2009-07-01

CF Chloroform Cl# Chlorine Number CO Carbon Monoxide CT Carbon Tetrachloride CVOC Chlorinated Volatile Organic Compound 1,2-DCA 1,2...As Safe HCl Hydrochloric Acid HRC® Hydrogen Release Compound IDW Investigation-Derived Waste ISCO In Situ Chemical Oxidation LEL Lower...Total Organic Carbon VC Vinyl Chloride VFA Volatile Fatty Acid VOC Volatile Organic Compound ZVI Zero Valent Iron viii ACKNOWLEDGEMENTS

The meteoritic record of presolar and early solar system organic chemistry. [Abstract only

NASA Technical Reports Server (NTRS)

Cronin, John R.; Pizzarello, Sandra

1994-01-01

Carbon, hydrogen, and nitrogen isotopic analyses of various classes of organic compounds done in collaboration with Epstein and Krishnamurthy (Caltech) have shown these compounds to be enriched to varying degrees in the heavier isotopes. These results, in particular the large deuterium enrichments, have been interpreted as indicating an interstellar origin for the meteorite compounds or their precursors. Such isotopic fractionations, of hydrogen especially, are characteristic of low temperature ion-molecule reactions in cold interstellar clouds. There is also evidence from the large corresponding suites of alpha-amino and alpha-hydroxy acids found in meteorites suggesting that aqueous phase chemistry on the meteorite parent body played an important role in the formation of these compounds. These data support the hypothesis that interstellar compounds survived in the solar nebula at a radial distance corresponding to the asteroid belt, were incorporated into the parent body in icy, volatile-rich, planetesinals, and underwent further reactions during a period of aqueous activity within the early parent body to give the present suite of meteorite compounds. This formation hypothesis will be discussed and the results of recent isotopic and molecular analyses bearing on it will be presented.

Occurrence and abatement of volatile sulfur compounds during biogas production.

PubMed

Andersson, Fräs Annika T; Karlsson, Anna; Svensson, Bo H; Ejlertsson, Jörgen

2004-07-01

Volatile sulfur compounds (VSCs) in biogas originating from a biogas production plant and from a municipal sewage water treatment plant were identified. Samples were taken at various stages of the biogas-producing process, including upgrading the gas to vehicle-fuel quality. Solid-phase microextraction was used for preconcentration of the VSCs, which were subsequently analyzed using gas chromatography in combination with mass spectrometry. Other volatile organic compounds present also were identified. The most commonly occurring VSCs in the biogas were hydrogen sulfide, carbonyl sulfide, methanethiol, dimethyl sulfide, and dimethyl disulfide, and hydrogen sulfide was not always the most abundant sulfur (S) compound. Besides VSCs, oxygenated organic compounds were commonly present (e.g., ketones, alcohols, and esters). The effect of adding iron chloride to the biogas reactor on the occurrence of VSCs also was investigated. It was found that additions of 500-g/m3 substrate gave an optimal removal of VSCs. Also, the use of a prefermentation step could reduce the amount of VSCs formed in the biogas process. Moreover, in the carbon dioxide scrubber used for upgrading the gas, VSCs were removed efficiently, leaving traces (ppbv levels). The scrubber also removed other organic compounds.

The Molecular Mechanism of the Catalase-like Activity in Horseradish Peroxidase.

PubMed

Campomanes, Pablo; Rothlisberger, Ursula; Alfonso-Prieto, Mercedes; Rovira, Carme

2015-09-02

Horseradish peroxidase (HRP) is one of the most relevant peroxidase enzymes, used extensively in immunochemistry and biocatalysis applications. Unlike the closely related catalase enzymes, it exhibits a low activity to disproportionate hydrogen peroxide (H2O2). The origin of this disparity remains unknown due to the lack of atomistic information on the catalase-like reaction in HRP. Using QM(DFT)/MM metadynamics simulations, we uncover the mechanism for reduction of the HRP Compound I intermediate by H2O2 at atomic detail. The reaction begins with a hydrogen atom transfer, forming a peroxyl radical and a Compound II-like species. Reorientation of the peroxyl radical in the active site, concomitant with the transfer of the second hydrogen atom, is the rate-limiting step, with a computed free energy barrier (18.7 kcal/mol, ∼ 6 kcal/mol higher than the one obtained for catalase) in good agreement with experiments. Our simulations reveal the crucial role played by the distal pocket residues in accommodating H2O2, enabling formation of a Compound II-like intermediate, similar to catalases. However, out of the two pathways for Compound II reduction found in catalases, only one is operative in HRP. Moreover, the hydrogen bond network in the distal side of HRP compensates less efficiently than in catalases for the energetic cost required to reorient the peroxyl radical at the rate-determining step. The distal Arg and a water molecule in the "wet" active site of HRP have a substantial impact on the reaction barrier, compared to the "dry" active site in catalase. Therefore, the lower catalase-like efficiency of heme peroxidases compared to catalases can be directly attributed to the different distal pocket architecture, providing hints to engineer peroxidases with a higher rate of H2O2 disproportionation.

Three closely related 4,5,6,7-tetrahydro-1H-pyrazolo[4,3-c]pyridines: synthesis, molecular conformations and hydrogen bonding in zero, one and two dimensions.

PubMed

Sagar, Belakavadi K; Harsha, Kachigere B; Yathirajan, Hemmige S; Rangappa, Kanchugarakoppal S; Rathore, Ravindranath S; Glidewell, Christopher

2017-03-01

In each of 1-(4-fluorophenyl)-5-methylsulfonyl-3-[4-(trifluoromethyl)phenyl]-4,5,6,7-tetrahydro-1H-pyrazolo[4,3-c]pyridine, C 21 H 19 F 4 N 3 O 2 S, (I), 1-(4-chlorophenyl)-5-methylsulfonyl-3-[4-(trifluoromethyl)phenyl]-4,5,6,7-tetrahydro-1H-pyrazolo[4,3-c]pyridine, C 21 H 19 ClF 3 N 3 O 2 S, (II), and 1-(3-methylphenyl)-5-methylsulfonyl-3-[4-(trifluoromethyl)phenyl]-4,5,6,7-tetrahydro-1H-pyrazolo[4,3-c]pyridine, C 22 H 22 F 3 N 3 O 2 S, (III), the reduced pyridine ring adopts a half-chair conformation with the methylsulfonyl substituent occupying an equatorial site. Although compounds (I) and (II) are not isostructural, having the space groups Pbca and P2 1 2 1 2 1 , respectively, their molecular conformations are very similar, but the conformation of compound (III) differs from those of (I) and (II) in the relative orientation of the N-benzyl and methylsulfonyl substituents. In compounds (II) and (III), but not in (I), the trifluoromethyl groups are disordered over two sets of atomic sites. Molecules of (I) are linked into centrosymmetric dimers by C-H...π(arene) hydrogen bonds, molecules of (II) are linked by two C-H...O hydrogen bonds to form ribbons of R 3 3 (18) rings, which are themselves further linked by a C-Cl...π(arene) interaction, and a combination of C-H...O and C-H...π(arene) hydrogen bonds links the molecules of (III) into sheets. Comparisons are made with the structures of some related compounds.

Improved solubility and bioactivity of theophylline (a bronchodilator drug) through its new nitrate salt analysed by experimental and theoretical approaches

NASA Astrophysics Data System (ADS)

Mary Novena, L.; Suresh Kumar, S.; Athimoolam, S.

2016-07-01

Synthesis, crystal structure, vibrational spectroscopy, quantum chemical studies and biological activity of the new semi organic compound, Theophyllinium Nitrate [C7H9N4 O2)+. (NO3)-], are reported here. Crystals of Theophyllinium nitrate (TN) were grown by slow solvent evaporation technique. The crystal packing is dominated by N-H···O intermolecular hydrogen bonds. The cations and anions are aggregated almost parallel leading to a lamellar structure. This molecular aggregation features two alternate hydrogen bonded chain C22(8) and C21(6) motifs. Further, a bifurcated ring R12(4) motifs is also seen. This aggregated molecular sheets are parallel to (2 bar 06) and (20 6 bar) planes of the crystal. The solubility test is carried out to enhance the physico-chemical activity of the compound. The atomic charge distribution on different atoms of TN has been calculated by Mulliken charge analysis. A detailed interpretation of FT-IR and FT-Raman spectra of TN show that most of the bands are matching between the experimental and theoretical methods. The strong intensity bands and shifting of bands due to intermolecular hydrogen bonds are also investigated. The NBO analysis is carried out to elucidate the stability of the molecule and charge delocalization within the molecule. The HOMO-LUMO analysis reveals molecular stability and chemical reactivity of the present compound. Also, the compound was examined for its antibacterial activity and found to exhibit notable activity against Pseudomonas aeruginosa. This shows that the present compound is a good candidate for the antimicrobial agent apart from its inherent Bronchodilator drug property. Hence, the new compound (TN) may be a good alternative for patients with Chronic Obstructive Pulmonary Disease (COPD) and bacterial infections.

Method of enhancing the electronic properties of an undoped and/or N-type hydrogenated amorphous silicon film

DOEpatents

Carlson, David E.

1980-01-01

The dark conductivity and photoconductivity of an N-type and/or undoped hydrogenated amorphous silicon layer fabricated by an AC or DC proximity glow discharge in silane can be increased through the incorporation of argon in an amount from 10 to about 90 percent by volume of the glow discharge atmosphere which contains a silicon-hydrogen containing compound in an amount of from about 90 to about 10 volume percent.

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

Chen, Wei; Rosser, Ethan W.; Zhang, Di

Hydrogen polysulfides (H 2S n, n>1) have been recently suggested to be the actual signalling molecules that involved in sulfur-related redox biology. However the exact mechanisms of H 2S n are still poorly understood and a major hurdle in this field is the lack of reliable and convenient methods for H 2S n detection. In this work we report a unique ring-opening reaction of N-sulfonylaziridine by Na 2S 2 under mild conditions. Based on this reaction a novel H 2S n-specific fluorescent probe (AP) was developed. The probe showed high sensitivity and selectivity for H 2S n. Notably, the fluorescentmore » turn-on product, i.e. compound 1, exhibited excellent two-photon photophysical properties and a large Stokes shift. Moreover, the high solid state luminescent efficiency of compound 1 makes it a potential candidate for organic emitters and solid-state lighting devices.« less

The Role of Hydrogen for Sulfurimonas denitrificans’ Metabolism

PubMed Central

Han, Yuchen; Perner, Mirjam

2014-01-01

Sulfurimonas denitrificans was originally isolated from coastal marine sediments. It can grow with thiosulfate and nitrate or sulfide and oxygen. Recently sequencing of its genome revealed that it encodes periplasmic and cytoplasmic [NiFe]-hydrogenases but the role of hydrogen for its metabolism has remained unknown. We show the first experimental evidence that S. denitrificans can indeed express a functional hydrogen uptake active hydrogenase and can grow on hydrogen. In fact, under the provided conditions it grew faster and denser on hydrogen than on thiosulfate alone and even grew with hydrogen in the absence of reduced sulfur compounds. In our experiments, at the time points tested, the hydrogen uptake activity appeared to be related to the periplasmic hydrogenase and not to the cytoplasmic hydrogenase. Our data suggest that under the provided conditions S. denitrificans can grow more efficiently with hydrogen than with thiosulfate. PMID:25170905

Methods of Forming Visual Hydrogen Detector with Variable Reversibility

NASA Technical Reports Server (NTRS)

Muradov, Nazim Z. (Inventor)

2014-01-01

Methods, processes and compositions are provided for a visual or chemochromic hydrogen-detector with variable or tunable reversible color change. The working temperature range for the hydrogen detector is from minus 100 C to plus 500 C. A hydrogen-sensitive pigment, including, but not limited to, oxides, hydroxides and polyoxo-compounds of tungsten, molybdenum, vanadium, chromium and combinations thereof, is combined with nano-sized metal activator particles and preferably, coated on a porous or woven substrate. In the presence of hydrogen, the composition rapidly changes its color from white or light-gray or light-tan to dark gray, navy-blue or black depending on the exposure time and hydrogen concentration in the medium. After hydrogen exposure ceases, the original color of the hydrogen-sensitive pigment is restored, and the visual hydrogen detector can be used repeatedly. By changing the composition of the hydrogen-sensitive pigment, the time required for its complete regeneration is varied from a few seconds to several days.

Visual hydrogen detector with variable reversibility

NASA Technical Reports Server (NTRS)

Muradov, Nazim (Inventor)

2011-01-01

Methods, processes and compositions are provided for a visual or chemochromic hydrogen-detector with variable or tunable reversible color change. The working temperature range for the hydrogen detector is from minus 100.degree. C. to plus 500.degree. C. A hydrogen-sensitive pigment, including, but not limited to, oxides, hydroxides and polyoxo-compounds of tungsten, molybdenum, vanadium, chromium and combinations thereof, is combined with nano-sized metal activator particles and preferably, coated on a porous or woven substrate. In the presence of hydrogen, the composition rapidly changes its color from white or light-gray or light-tan to dark gray, navy-blue or black depending on the exposure time and hydrogen concentration in the medium. After hydrogen exposure ceases, the original color of the hydrogen-sensitive pigment is restored, and the visual hydrogen detector can be used repeatedly. By changing the composition of the hydrogen-sensitive pigment, the time required for its complete regeneration is varied from a few seconds to several days.

Visual hydrogen detector with variable reversibilty

NASA Technical Reports Server (NTRS)

Muradov, Nazim Z. (Inventor)

2012-01-01

Methods, processes and compositions are provided for a visual or chemochromic hydrogen-detector with variable or tunable reversible color change. The working temperature range for the hydrogen detector is from minus 100.degree. C. to plus 500.degree. C. A hydrogen-sensitive pigment, including, but not limited to, oxides, hydroxides and polyoxo-compounds of tungsten, molybdenum, vanadium, chromium and combinations thereof, is combined with nano-sized metal activator particles and preferably, coated on a porous or woven substrate. In the presence of hydrogen, the composition rapidly changes its color from white or light-gray or light-tan to dark gray, navy-blue or black depending on the exposure time and hydrogen concentration in the medium. After hydrogen exposure ceases, the original color of the hydrogen-sensitive pigment is restored, and the visual hydrogen detector can be used repeatedly. By changing the composition of the hydrogen-sensitive pigment, the time required for its complete regeneration is varied from a few seconds to several days.

Chromatographic hydrogen isotope separation

DOEpatents

Aldridge, Frederick T.

1981-01-01

Intermetallic compounds with the CaCu.sub.5 type of crystal structure, particularly LaNiCo.sub.4 and CaNi.sub.5, exhibit high separation factors and fast equilibrium times and therefore are useful for packing a chromatographic hydrogen isotope separation colum. The addition of an inert metal to dilute the hydride improves performance of the column. A large scale mutli-stage chromatographic separation process run as a secondary process off a hydrogen feedstream from an industrial plant which uses large volumes of hydrogen can produce large quantities of heavy water at an effective cost for use in heavy water reactors.

Diethyl [(4-bromo­phen­yl)(5-chloro-2-hydroxy­anilino)meth­yl]phospho­nate

PubMed Central

Babu, V. H. H. Surendra; Krishnaiah, M.; Prasad, G. Syam; C. Suresh Reddy; Kant, Rajni

2009-01-01

In the title compound, C17H20BrClNO4P, inter­molecular C—H⋯O and N—H⋯O hydrogen bonds form centrosymmetric R 2 2(10) dimers linked through O—H⋯O inter­molecular hydrogen bonds, which form centrosymmetric R 2 2(16) dimers. All these hydrogen bonds form chains along [010]. In addition, the crystal structure is stabilized by weak C—H⋯Br hydrogen bonds. The very weak intramolecular N—H⋯O interaction forms a five-membered ring. PMID:21578446

Kinetics and models of hydrogenation of phenylhydroxylamine and azobenzene on nickel catalysts in aqueous 2-propanol solutions

NASA Astrophysics Data System (ADS)

Romanenko, Yu. E.; Merkin, A. A.; Komarov, A. A.; Lefedova, O. V.

2014-08-01

The kinetics of the hydrogenation of intermediates in the reduction of nitrobenzene in aqueous 2-propanol with acetic acid and sodium hydroxide additions on nickel catalysts was studied. A kinetic description of liquid-phase hydrogenation of azobenzene and phenylhydroxylamine was suggested. A kinetic model was developed. The dependences that characterize the variation of the amounts of the starting compound, reaction product, and absorbed hydrogen during the reaction were calculated. The calculated values were shown to be in satisfactory agreement with the experimental values under different reaction conditions.

Chromatographic hydrogen isotope separation

DOEpatents

Aldridge, F.T.

Intermetallic compounds with the CaCu/sub 5/ type of crystal structure, particularly LaNiCo/sub 4/ and CaNi/sub 5/, exhibit high separation factors and fast equilibrium times and therefore are useful for packing a chromatographic hydrogen isotope separation column. The addition of an inert metal to dilute the hydride improves performance of the column. A large scale multi-stage chromatographic separation process run as a secondary process off a hydrogen feedstream from an industrial plant which uses large volumes of hydrogen cn produce large quantities of heavy water at an effective cost for use in heavy water reactors.

N-(1,3-Thia­zol-2-yl)benzamide

PubMed Central

Zonouzi, Afsaneh; Mirzazadeh, Roghieh; Rahmani, Hossein; Ng, Seik Weng

2009-01-01

The title compound, C10H8N2OS, features a nonplanar mol­ecule [dihedral angle between the two aromatic rings = 43.6 (1)°]. Two mol­ecules are linked by N—H⋯N hydrogen bonds about a centre of inversion, giving rise to a hydrogen-bonded dimer. PMID:21582538

Computational Studies Of Chemical Reactions: The Hnc-Hcn And Ch[subscript3]Nc-Ch[subscript3]Cn Isomerizations

ERIC Educational Resources Information Center

Halpern, Arthur M.

2006-01-01

The application of computational methods to the isomerization of hydrogen isocyanide to hydrogen cyanide, HNC-HCN is described. The logical extension to the exercise is presented to the isomerization of the methyl-substituted compounds, methylisocyanide and methylcyanide, Ch[subscript 3]NC-CH[subscript3]CN.

1,5-Bis[1-(2,4-dihy­droxy­phen­yl)ethyl­idene]carbonohydrazide dimethyl­formamide disolvate

PubMed Central

He, Qing-Peng; Tan, Bo; Lu, Ze-Hua

2010-01-01

In the title compound, C17H18N4O5·2C3H7NO, two solvent mol­ecules are linked to the main mol­ecule via N—H⋯O and O—H⋯O hydrogen bonds, forming a hydrogen-bonded trimer. Intra­molecular O—H⋯N hydrogen bonds influence the mol­ecular conformation of the main mol­ecule, and the two benzene rings form a dihedral angle of 10.55 (18)°. In the crystal, inter­molecular O—H⋯O hydrogen bonds link hydrogen-bonded trimers into ribbons extending along the b axis. PMID:21589135

Co-treatment of hydrogen sulfide and methanol in a single-stage biotrickling filter under acidic conditions.

PubMed

Jin, Yaomin; Veiga, María C; Kennes, Christian

2007-06-01

Biofiltration of waste gases is cost-effective and environment-friendly compared to the conventional techniques for treating large flow rates of gas streams with low concentrations of pollutants. Pulp and paper industry off-gases usually contain reduced sulfur compounds, such as hydrogen sulfide and a wide range of volatile organic compounds (VOCs), e.g., methanol. It is desirable to eliminate both of these groups of compounds. Since the co-treatment of inorganic sulfur compounds and VOCs in biotrickling filters is a relatively unexplored area, the simultaneous biotreatment of H2S and methanol as the model VOC was investigated. The results showed that, after adaptation, the elimination capacity of methanol could reach around 236 g m(-3) h(-1) with the simultaneous complete removal (100%) of 12 ppm H2S when the empty bed residence time is 24 s. The pH of the system was around 2. Methanol removal was hardly affected by the presence of hydrogen sulfide, despite the low pH. Conversely, the presence of the VOC in the waste gas reduced the efficiency of H2S biodegradation. The maximal methanol removal decreased somewhat when increasing the gas flow rate. This is the first report on the degradation of methanol at such low pH in a biotrickling filter and on the co-treatment of H2S and VOCs under such conditions.

Simultaneous treatment of dimethyl disulfide and hydrogen sulfide in an alkaline biotrickling filter.

PubMed

Arellano-García, Luis; Le Borgne, Sylvie; Revah, Sergio

2018-01-01

Foul odors comprise generally a complex mixture of molecules, where reduced sulfur compounds play a key role due to their toxicity and low odor threshold. Previous reports on treating mixtures of sulfur compounds in single biofilters showed that hydrogen sulfide (H 2 S) interferes with the removal and degradation of other sulfur compounds. In this study, hydrogen sulfide (H 2 S) and dimethyl disulfide (DMDS) were fed to an alkaline biotrickling filter (ABTF) at pH 10, to evaluate the simultaneous removal of inorganic and organic sulfur compounds in a single, basic-pH system. The H 2 S-DMDS mixture was treated for more than 200 days, with a gas residence time of 40 s, attaining elimination capacities of 86 g DMDS m -3 h -1 and 17 g H2S m -3 h -1 and removal efficiencies close to 100%. Conversion of H 2 S and DMDS to sulfate was generally above 70%. Consumption of sulfide and formaldehyde was verified by respirometry, suggesting the coexistence of both methylotrophic and chemoautotrophic breakdown pathways by the immobilized alkaliphilic biomass. The molecular biology analysis showed that the long-term acclimation of the ABTF led to a great variety of bacteria, predominated by Thioalkalivibrio species, while fungal community was notoriously less diverse and dominated by Fusarium species. Copyright © 2017. Published by Elsevier Ltd.

Synthesis and crystal structures of coordination compounds of pyridoxine with zinc and cadmium sulfates

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

Furmanova, N. G., E-mail: furm@ns.crys.ras.ru; Berdalieva, Zh. I., E-mail: kakin@inbox.ru; Chernaya, T. S.

2009-03-15

The pyridoxine complexes with zinc and cadmium sulfates are synthesized. The IR absorption spectra and thermal behavior of the synthesized compounds are described. Crystals of the [M(C{sub 8}H{sub 11}O{sub 3}N){sub 2}(H{sub 2}O){sub 2}]SO{sub 4} . 3H{sub 2}O (M = Zn, Cd) compounds are investigated using X-ray diffraction. In the structures of both compounds, the M atoms are coordinated by the oxygen atoms of the deprotonated OH group and the CH{sub 2}OH group retaining its own hydrogen atom, as well as by two H{sub 2}O molecules, and have an octahedral coordination. The nitrogen atom of the heterocycle is protonated, so thatmore » the heterocycle acquires a pyridinium character. The cationic complexes form layers separated by the anions and crystallization water molecules located in between. The structural units of the crystals are joined together by a complex system of hydrogen bonds.« less

Antioxidant activity, total phenolics and flavonoids contents: Should we ban in vitro screening methods?

PubMed

Granato, Daniel; Shahidi, Fereidoon; Wrolstad, Ronald; Kilmartin, Paul; Melton, Laurence D; Hidalgo, Francisco J; Miyashita, Kazuo; Camp, John van; Alasalvar, Cesarettin; Ismail, Amin B; Elmore, Stephen; Birch, Gordon G; Charalampopoulos, Dimitris; Astley, Sian B; Pegg, Ronald; Zhou, Peng; Finglas, Paul

2018-10-30

As many studies are exploring the association between ingestion of bioactive compounds and decreased risk of non-communicable diseases, the scientific community continues to show considerable interest in these compounds. In addition, as many non-nutrients with putative health benefits are reducing agents, hydrogen donors, singlet oxygen quenchers or metal chelators, measurement of antioxidant activity using in vitro assays has become very popular over recent decades. Measuring concentrations of total phenolics, flavonoids, and other compound (sub)classes using UV/Vis spectrophotometry offers a rapid chemical index, but chromatographic techniques are necessary to establish structure-activity. For bioactive purposes, in vivo models are required or, at the very least, methods that employ distinct mechanisms of action (i.e., single electron transfer, transition metal chelating ability, and hydrogen atom transfer). In this regard, better understanding and application of in vitro screening methods should help design of future research studies on 'bioactive compounds'. Copyright © 2018 Elsevier Ltd. All rights reserved.

[Regulation of sulfates, hydrogen sulfide and heavy metals in technogenic reservoirs by sulfate-reducing bacteria].

PubMed

Hudz', S P; Peretiatko, T B; Moroz, O M; Hnatush, S O; Klym, I R

2011-01-01

Sulfate-reducing bacteria Desulfovibrio desulfuricans Ya-11 in the presence of sulfates and organic compounds in the medium reduce sulfates to hydrogen sulfide (dissimilatory sulfate reduction). Heavy metals in concentration over 2 mM inhibit this process. Pb2+, Zn2+, Ni2+, Co2+, Fe2+ and Cd2+ ions in concentration 1-1.5 mM display insignificant inhibiting effect on sulfate reduction process, and metals precipitate in the form of sulfides. At concentrations of heavy metals 2-3 mM one can observe a decrease of sulfates reduction intensity, and a percent of metals binding does not exceed 72%. Obtained results give reason to confirm, that sulfate-reducing bacteria play an important role in regulation of the level of sulfates, hydrogen sulfide and heavy metals in reservoirs and they may be used for purification of water environment from these compounds.

Pillared montmorillonite catalysts for coal liquefaction

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

Sharma, R.K.; Olson, E.S.

1994-12-31

Pillared clays contain large micropores and have considerable potential for catalytic hydrogenation and cleavage of coal macromolecules. Pillared montmorillonite-supported catalysts were prepared by the intercalation of polynuclear hydroxychromium cations and subsequent impregnation of nickel and molybdenum. Infrared and thermogravimetric studies of pyridine-adsorbed catalysts indicated the presence of both Lewis and Bronsted acid sites. Thus, the catalysts have both acidic properties that can aid in hydrocracking and cleavage of carbon-heteroatom bonds as well as hydrogen-activating bimetallic sites. These catalysts were applied to the hydrodesulfurization and liquefaction of coal-derived intermediates. The reactions of model organosulfur compounds and coal liquids were carried outmore » at 300{degrees}-400{degrees}C for 3 hours in the presence of 1000 psi of molecular hydrogen. Reaction products were analyzed by GC/FT-IR/MS/AED. The catalysts have been found to be very effective in removing sulfur from model compounds as well as liquefaction products.« less

Catalytic two-stage coal liquefaction process having improved nitrogen removal

DOEpatents

Comolli, Alfred G.

1991-01-01

A process for catalytic multi-stage hydrogenation and liquefaction of coal to produce high yields of low-boiling hydrocarbon liquids containing low concentrations of nitogen compounds. First stage catalytic reaction conditions are 700.degree.-800.degree. F. temperature, 1500-3500 psig hydrogen partial pressure, with the space velocity maintained in a critical range of 10-40 lb coal/hr ft.sup.3 catalyst settled volume. The first stage catalyst has 0.3-1.2 cc/gm total pore volume with at least 25% of the pore volume in pores having diameters of 200-2000 Angstroms. Second stage reaction conditions are 760.degree.-870.degree. F. temperature with space velocity exceeding that in the first stage reactor, so as to achieve increased hydrogenation yield of low-boiling hydrocarbon liquid products having at least 75% removal of nitrogen compounds from the coal-derived liquid products.

Investigation of non-covalent and hydrogen bonding interactions on the formation of crystalline networks and supramolecular synthons of a series of α-aminophosphonates: Crystallography and DFT studies

NASA Astrophysics Data System (ADS)

Mirzaei, Masoud; Eshghi, Hossein; Akhlaghi Bagherjeri, Fateme; Mirzaei, Mahdi; Farhadipour, Abolghasem

2018-07-01

α-Aminophosphonates have been rarely explored in the field of crystal engineering. These organic molecules are capable of forming reliable and reproducible supramolecular synthons through non-covalent interactions that can be employed for designing high dimensional supramolecular architectures. Here, we systematically study the influence of conventional and unconventional hydrogen bonding interactions on the formation of these synthons and stability of the crystal packing. The theoretical studies were employed to further confirm the presence of these synthons by comparing the stabilization energies of the dimers and monomers. The dependence of the stability of NH⋯O hydrogen bonds to the aromatic substituents were investigated using NBO analysis. The most stable compound was determined by comparing the HOMO-LUMO energy gap of all compounds and compared with NBO analysis.

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

Kang, Dongseok; Young, James L.; Lim, Haneol

Despite their excellent photophysical properties and record-high solar-to-hydrogen conversion efficiency, the high cost and limited stability of III-V compound semiconductors prohibit their practical application in solar-driven photoelectrochemical water splitting. Here in this paper we present a strategy for III-V photocatalysis that can circumvent these difficulties via printed assemblies of epitaxially grown compound semiconductors. A thin film stack of GaAs-based epitaxial materials is released from the growth wafer and printed onto a non-native transparent substrate to form an integrated photocatalytic electrode for solar hydrogen generation. The heterogeneously integrated electrode configuration together with specialized epitaxial design serve to decouple the material interfacesmore » for illumination and electrocatalysis. Subsequently, this allows independent control and optimization of light absorption, carrier transport, charge transfer, and material stability. Using this approach, we construct a series-connected wireless tandem system of GaAs photoelectrodes and demonstrate 13.1% solar-to-hydrogen conversion efficiency of unassisted-mode water splitting.« less

Identification and in silico prediction of metabolites of the model compound, tebufenozide by human CYP3A4 and CYP2C19.

PubMed

Shirotani, Naoki; Togawa, Moe; Ikushiro, Shinichi; Sakaki, Toshiyuki; Harada, Toshiyuki; Miyagawa, Hisashi; Matsui, Masayoshi; Nagahori, Hirohisa; Mikata, Kazuki; Nishioka, Kazuhiko; Hirai, Nobuhiro; Akamatsu, Miki

2015-10-15

The metabolites of tebufenozide, a model compound, formed by the yeast-expressed human CYP3A4 and CYP2C19 were identified to clarify the substrate recognition mechanism of the human cytochrome P450 (CYP) isozymes. We then determined whether tebufenozide metabolites may be predicted in silico. Hydrogen abstraction energies were calculated with the density functional theory method B3LYP/6-31G(∗). A docking simulation was performed using FRED software. Several alkyl sites of tebufenozide were hydroxylated by CYP3A4 whereas only one site was modified by CYP2C19. The accessibility of each site of tebufenozide to the reaction center of CYP enzymes and the susceptibility of each hydrogen atom for metabolism by CYP enzymes were evaluated by a docking simulation and hydrogen abstraction energy estimation, respectively. Copyright © 2015 Elsevier Ltd. All rights reserved.

Photodegradation of polycyclic aromatic hydrocarbons in soils under a climate change base scenario.

PubMed

Marquès, Montse; Mari, Montse; Audí-Miró, Carme; Sierra, Jordi; Soler, Albert; Nadal, Martí; Domingo, José L

2016-04-01

The photodegradation of polycyclic aromatic hydrocarbons (PAHs) in two typical Mediterranean soils, either coarse- or fine-textured, was here investigated. Soil samples, spiked with the 16 US EPA priority PAHs, were incubated in a climate chamber at stable conditions of temperature (20 °C) and light (9.6 W m(-2)) for 28 days, simulating a climate change base scenario. PAH concentrations in soils were analyzed throughout the experiment, and correlated with data obtained by means of Microtox(®) ecotoxicity test. Photodegradation was found to be dependent on exposure time, molecular weight of each hydrocarbon, and soil texture. Fine-textured soil was able to enhance sorption, being PAHs more photodegraded than in coarse-textured soil. According to the EC50 values reported by Microtox(®), a higher detoxification was observed in fine-textured soil, being correlated with the outcomes of the analytical study. Significant photodegradation rates were detected for a number of PAHs, namely phenanthrene, anthracene, benzo(a)pyrene, and indeno(123-cd)pyrene. Benzo(a)pyrene, commonly used as an indicator for PAH pollution, was completely removed after 7 days of light exposure. In addition to the PAH chemical analysis and the ecotoxicity tests, a hydrogen isotope analysis of benzo(a)pyrene was also carried out. The degradation of this specific compound was associated to a high enrichment in (2)H, obtaining a maximum δ(2)H isotopic shift of +232‰. This strong isotopic effect observed in benzo(a)pyrene suggests that compound-specific isotope analysis (CSIA) may be a powerful tool to monitor in situ degradation of PAHs. Moreover, hydrogen isotopes of benzo(a)pyrene evidenced a degradation process of unknown origin occurring in the darkness. Copyright © 2016 Elsevier Ltd. All rights reserved.

Triple-element compound-specific stable isotope analysis of 1,2-dichloroethane for characterization of the underlying dehalogenation reaction in two Dehalococcoides mccartyi strains.

PubMed

Franke, Steffi; Lihl, Christina; Renpenning, Julian; Elsner, Martin; Nijenhuis, Ivonne

2017-12-01

Chlorinated ethanes belong to the most common groundwater and soil contaminants. Of these, 1,2-dichloroethane (1,2-DCA) is a man-made, persistent and toxic contaminant, released due to improper waste treatment at versatile production sites. This study investigated the anaerobic transformation of 1,2-DCA by Dehalococcoides mccartyi strain 195 and strain BTF08 using triple-element compound-specific stable isotope analysis of carbon, chlorine and hydrogen for the first time. Isotope fractionation patterns for carbon (εCBTF08 = -28.4 ± 3.7‰; εC195 = -30.9 ± 3.6‰) and chlorine (εClBTF08 = -4.6 ± 0.7‰; εCl195 = -4.2 ± 0.5‰) within both investigated D. mccartyi strains, as well as the dual-element analysis (ΛBTF08 = 6.9 ± 1.2; Λ195 = 7.1 ± 0.2), supported identical reaction mechanisms for dehalogenation of 1,2-DCA. Hydrogen isotope fractionation analysis revealed dihaloelimination as prevalent reaction mechanism. Vinyl chloride as major intermediate could be excluded by performing the experiment in deuterated aqueous media. Furthermore, evaluation of the derived apparent kinetic isotope effects (AKIECBTF08 = 1.029/AKIEC195 = 1.031; AKIEClBTF08 = 1.005/AKIECl195 = 1.004) pointed towards simultaneous abstraction of both involved chlorine-substituents in a concerted matter. It was shown that D. mccartyi strain BTF08 and strain 195 are capable of complete, direct dihaloelimination of 1,2-DCA to ethene. © FEMS 2017. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

Nature and composition of fat bloom from palm kernel stearin and hydrogenated palm kernel stearin compound chocolates.

PubMed

Smith, Kevin W; Cain, Fred W; Talbot, Geoff

2004-08-25

Palm kernel stearin and hydrogenated palm kernel stearin can be used to prepare compound chocolate bars or coatings. The objective of this study was to characterize the chemical composition, polymorphism, and melting behavior of the bloom that develops on bars of compound chocolate prepared using these fats. Bars were stored for 1 year at 15, 20, or 25 degrees C. At 15 and 20 degrees C the bloom was enriched in cocoa butter triacylglycerols, with respect to the main fat phase, whereas at 25 degrees C the enrichment was with palm kernel triacylglycerols. The bloom consisted principally of solid fat and was sharper melting than was the fat in the chocolate. Polymorphic transitions from the initial beta' phase to the beta phase accompanied the formation of bloom at all temperatures.

Design of specific peptide inhibitors of phospholipase A2: structure of a complex formed between Russell's viper phospholipase A2 and a designed peptide Leu-Ala-Ile-Tyr-Ser (LAIYS).

PubMed

Chandra, Vikas; Jasti, Jayasankar; Kaur, Punit; Dey, Sharmistha; Srinivasan, A; Betzel, Ch; Singh, T P

2002-10-01

Phospholipase A(2) (EC 3.1.1.4) is a key enzyme of the cascade mechanism involved in the production of proinflammatory compounds known as eicosanoids. The binding of phospholipase A(2) to membrane surfaces and the hydrolysis of phospholipids are thought to involve the formation of a hydrophobic channel into which a single substrate molecule diffuses before cleavage. In order to regulate the production of proinflammatory compounds, a specific peptide inhibitor of PLA(2), Leu-Ala-Ile-Tyr-Ser, has been designed. Phospholipase A(2) from Daboia russelli pulchella (DPLA(2)) and peptide Leu-Ala-Ile-Tyr-Ser (LAIYS) have been co-crystallized. The structure of the complex has been determined and refined to 2.0 A resolution. The structure contains two crystallographically independent molecules of DPLA(2), with one molecule of peptide specifically bound to one of them. The overall conformations of the two molecules are essentially similar except in three regions; namely, the calcium-binding loop including Trp31 (residues 25-34), the beta-wing consisting of two antiparallel beta-strands (residues 74-85) and the C-terminal region (residues 119-133). Of these, the most striking difference pertains to the orientation of Trp31 in the two molecules. The conformation of Trp31 in molecule A was suitable to allow the binding of peptide LAIYS, while that in molecule B prevented the entry of the ligand into the hydrophobic channel. The structure of the complex clearly showed that the OH group of Tyr of the inhibitor formed hydrogen bonds with both His48 N(delta1) and Asp49 O(delta1), while O(gamma)H of Ser was involved in a hydrogen bond with Trp31. Other peptide backbone atoms interact with protein through water molecules, while Leu, Ala and Ile form strong hydrophobic interactions with the residues of the hydrophobic channel.

Characterization of volatile sulfur compound production by Solobacterium moorei.

PubMed

Tanabe, Shin-ichi; Grenier, Daniel

2012-12-01

Solobacterium moorei is a Gram positive bacterium that has been specifically associated with halitosis. The aim of this study was to characterize volatile sulfur compound (VSC) production by S. moorei. S. moorei was either grown or incubated in the presence of various supplements prior to determining VSC production with a Halimeter sulfide monitor. The effect of exogenous proteases or glycosidase inhibitors on VSC production by S. moorei was examined. We first showed that S. moorei can convert cysteine into hydrogen sulfide. The capacity of S. moorei to produce VSCs from serum, saliva, and mucin was dependent on the presence of an exogenous source of proteases such as pancreatic trypsin or Porphyromonas gingivalis gingipains. VSC production from mucin was inhibited by the presence of a β-galactosidase inhibitor, thus suggesting that deglycosylation of mucin by S. moorei is critical for VSC production. Our study suggests that S. moorei can be a major source of malodorous compounds in halitosis by producing VSCs through a process involving the β-galactosidase activity of the bacterium and an exogenous source of proteases. Copyright © 2012 Elsevier Ltd. All rights reserved.

Modeling 3D-CSIA data: Carbon, chlorine, and hydrogen isotope fractionation during reductive dechlorination of TCE to ethene.

PubMed

Van Breukelen, Boris M; Thouement, Héloïse A A; Stack, Philip E; Vanderford, Mindy; Philp, Paul; Kuder, Tomasz

2017-09-01

Reactive transport modeling of multi-element, compound-specific isotope analysis (CSIA) data has great potential to quantify sequential microbial reductive dechlorination (SRD) and alternative pathways such as oxidation, in support of remediation of chlorinated solvents in groundwater. As a key step towards this goal, a model was developed that simulates simultaneous carbon, chlorine, and hydrogen isotope fractionation during SRD of trichloroethene, via cis-1,2-dichloroethene (and trans-DCE as minor pathway), and vinyl chloride to ethene, following Monod kinetics. A simple correction term for individual isotope/isotopologue rates avoided multi-element isotopologue modeling. The model was successfully validated with data from a mixed culture Dehalococcoides microcosm. Simulation of Cl-CSIA required incorporation of secondary kinetic isotope effects (SKIEs). Assuming a limited degree of intramolecular heterogeneity of δ 37 Cl in TCE decreased the magnitudes of SKIEs required at the non-reacting Cl positions, without compromising the goodness of model fit, whereas a good fit of a model involving intramolecular CCl bond competition required an unlikely degree of intramolecular heterogeneity. Simulation of H-CSIA required SKIEs in H atoms originally present in the reacting compounds, especially for TCE, together with imprints of strongly depleted δ 2 H during protonation in the products. Scenario modeling illustrates the potential of H-CSIA for source apportionment. Copyright © 2017 The Authors. Published by Elsevier B.V. All rights reserved.

Oxidation and detoxification of trivalent arsenic species.

PubMed

Aposhian, H Vasken; Zakharyan, Robert A; Avram, Mihaela D; Kopplin, Michael J; Wollenberg, Michael L

2003-11-15

Arsenic compounds with a +3 oxidation state are more toxic than analogous compounds with a +5 oxidation state, for example, arsenite versus arsenate, monomethylarsonous acid (MMA(III)) versus monomethylarsonic acid (MMA(V)), and dimethylarsinous acid (DMA(III)) versus dimethylarsinic acid (DMA(V)). It is no longer believed that the methylation of arsenite is the beginning of a methylation-mediated detoxication pathway. The oxidation of these +3 compounds to their less toxic +5 analogs by hydrogen peroxide needs investigation and consideration as a potential mechanism for detoxification. Xanthine oxidase uses oxygen to oxidize hypoxanthine to xanthine to uric acid. Hydrogen peroxide and reactive oxygen are also products. The oxidation of +3 arsenicals by the hydrogen peroxide produced in the xanthine oxidase reaction was blocked by catalase or allopurinol but not by scavengers of the hydroxy radical, e.g., mannitol or potassium iodide. Melatonin, the singlet oxygen radical scavenger, did not inhibit the oxidation. The production of H2O2 by xanthine oxidase may be an important route for decreasing the toxicity of trivalent arsenic species by oxidizing them to their less toxic pentavalent analogs. In addition, there are many other reactions that produce hydrogen peroxide in the cell. Although chemists have used hydrogen peroxide for the oxidation of arsenite to arsenate to purify water, we are not aware of any published account of its potential importance in the detoxification of trivalent arsenicals in biological systems. At present, this oxidation of the +3 oxidation state arsenicals is based on evidence from in vitro experiments. In vivo experiments are needed to substantiate the role and importance of H2O2 in arsenic detoxication in mammals.

Three-dimensional six-connecting organic building blocks based on polychlorotriphenylmethyl units--synthesis, self-assembly, and magnetic properties.

PubMed

Roques, Nans; Maspoch, Daniel; Wurst, Klaus; Ruiz-Molina, Daniel; Rovira, Concepció; Veciana, Jaume

2006-12-13

The synthesis of a three-dimensional, six-connecting, organic building block based on a robust, rigid, and open-shell polychlorotriphenylmethyl (PTM) unit (radical 1) is reported, and its self-assembly properties are described in detail. The tendencies of this highly polar molecule and its hydrogenated precursor, compound 4, to form hydrogen bonds with oxygenated solvents ([1THF(6)] and [4THF(6)]) were reduced by replacing THF with diethyl ether in the crystallization process to yield two-dimensional (2D) hydrogen-bonded structures ([1(Et(2)O)(3)] and [4(Et(2)O)(3)]). The presence of direct hydrogen bonds between the radicals in the latter phase of 1 gives rise to very weak ferromagnetic intermolecular interactions at low temperatures, whereas when the radicals are isolated by THF molecules these interactions are antiferromagnetic and very weak. The role played by the carboxylic groups not only in the self-assembly properties but also in the transmission of the magnetic interactions has been illustrated by determination of the crystal structure and measurement of the magnetic properties of the corresponding hexaester radical 6, in which the close packing of molecular units gives rise to weak antiferromagnetic intermolecular interactions. Attempts to avoid solvation of the molecules in the solid state and to increase the structural and magnetic dimensionality were pursued by recrystallization of both compounds 1 and 4 from concentrated nitric acid, affording two three-dimensional (3D) robust hydrogen-bonded structures. While the structure obtained with compound 4 is characterized by the presence of polar channels and boxes containing water guest molecules along the c axis, radical 1 was oxidized to the corresponding fuchsone 10, which presented a completely different close-packed, guest-free structure.

Boron-based dual imaging probes, compositions and methods for rapid aqueous F-18 labeling, and imaging methods using same

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

Li, Zibo; Gabbai, Francois P.; Conti, Peter S.

A composition useful as a PET and/or fluorescence imaging probe a compound a compound of Formula I, including salts, hydrates and solvates thereof: ##STR00001## wherein R.sub.1-R.sub.7 may be independently selected from hydrogen, halogen, hydroxy, alkoxy, nitro, substituted and unsubstituted amino, cycloalkyl, carboxy, carboxylic acids and esters thereof, cyano, haloalkyl, aryl, X is selected from the group consisting of C and N; and A is selected of hydrogen, halogen, hydroxy, alkoxy, nitro, substituted and unsubstituted amino, alkyl, cycloalkyl, carboxy, carboxylic acids and esters thereof, cyano, haloalkyl, aryl, including phenyl and aminophenyl, and heteroaryl.

The Crystal Structures of Potentially Tautomeric Compounds

NASA Astrophysics Data System (ADS)

Furmanova, Nina G.

1981-08-01

Data on the structures of potentially proto-, metallo-, and carbono-tropic compounds, obtained mainly by X-ray diffraction, are surveyed. The results of neutron and electron diffraction studies have also been partly used. It is shown that a characteristic feature of all the systems considered is the formation of hydrogen or secondary bonds ensuring the contribution of both possible tautomeric forms to the structure. Systematic consideration of the experimental data leads to the conclusion that there is a close relation between the crystal structure and the dynamic behaviour of the molecules in solution and that secondary and hydrogen bonds play a significant role in the tautomeric transition. The bibliography includes 152 references.

Synthesis of bulk chromium hydrides under pressure of up to 120 GPa

NASA Astrophysics Data System (ADS)

Marizy, Adrien; Geneste, Grégory; Loubeyre, Paul; Guigue, Bastien; Garbarino, Gaston

2018-05-01

Stable compounds in the Cr-H system have been synthesized through a direct reaction of chromium and hydrogen in a laser-heated diamond-anvil cell and investigated using synchrotron x-ray diffraction up to 120 GPa . The sequence of hydrides CrH, Cr2H3 , and CrH2 has been observed by increasing pressure. The known ɛ -h c p -CrH hydride is formed above 3 GPa . A Cr2H3 hydride with a C 2 /m structure appears spontaneously above 19 GPa , as a result of the filling of the tetrahedral sites of ɛ -CrH. YAG laser heating helps dissolve more hydrogen inside the h c p chromium structure to synthesize a CrH2 compound with a P n m a structure from 30 GPa on. The volume expansion per hydrogen atom in octahedral and tetrahedral sites is measured up to the 100-GPa pressure range. The formation pressures and structures of these chromium interstitial hydrides are in very good agreement with DFT calculations. However, despite multiple heating attempts up to 100 GPa , no evidence of the stability of the predicted CrH3 compound could be found.

Binding in alkali and alkaline-earth tetrahydroborates: Special position of magnesium tetrahydroborate

NASA Astrophysics Data System (ADS)

Łodziana, Zbigniew; van Setten, Michiel J.

2010-01-01

Compounds of light elements and hydrogen are currently extensively studied due to their potential application in the field of hydrogen or energy storage. A number of new interesting tetrahydroborates that are especially promising due to their very high gravimetric hydrogen content were recently reported. However, the determination and understanding of their complex crystalline structures has created considerable debate. Metal tetrahydroborates, in general, form a large variety of structures ranging from simple for NaBH4 to very complex for Mg(BH4)2 . Despite the extensive discussion in the literature no clear explanation has been offered for this variety so far. In this paper we analyze the structural and electronic properties of a broad range of metal tetrahydroborates and reveal the factors that determine their structure: ionic bonding, the orientation of the BH4 groups, and the coordination number of the metal cation. We show, in a simple way, that the charge transfer in the metal tetrahydroborates rationally explains the structural diversity of these compounds. Being ionic systems, the metal tetrahydroborates fall into the classification of Linus Pauling. By using the ionic radius for the BH4 group as determined in this paper, this allows for structural predictions for new and mixed compounds.

Structural, quantum chemical, vibrational and thermal studies of a hydrogen bonded zwitterionic co-crystal (nicotinic acid: pyrogallol)

NASA Astrophysics Data System (ADS)

Prabha, E. Arockia Jeya Yasmi; Kumar, S. Suresh; Athimoolam, S.; Sridhar, B.

2017-02-01

In the present work, a new co-crystal of nicotinic acid with pyrogallol (NICPY) has been grown in the zwitterionic form and the corresponding structural, vibrational, thermal, solubility and anti-cancer characteristics have been reported. The single crystal X-ray diffraction analysis confirms that the structural molecular packing of the crystal stabilized through N-H⋯O and O-H⋯O hydrogen bond. The stabilization energy of the hydrogen bond motifs were calculated in the solid state. Vibrational spectral studies such as Fourier transform-infrared (FT-IR) and FT-Raman were adopted to understand the zwitterionic co-crystalline nature of the compound, which has been compared with theoretically calculated vibrational frequencies. The thermal stability of the grown co-crystal was analyzed by TG/DTA study. The solubility of the NICPY co-crystal was investigated in water at different temperature and compared with that of the nicotinic acid, which is the parent compound of NICPY co-crystal. The grown crystals were treated with human cervical cancer cell line (HeLa) to analyze the cytotoxicity of NICPY crystals and compared with the parent compound, which shows that NICPY has moderate activity against human cervical cancer cell line.

Honeybees (Apis mellifera) learn to discriminate the smell of organic compounds from their respective deuterated isotopomers

PubMed Central

Gronenberg, Wulfila; Raikhelkar, Ajay; Abshire, Eric; Stevens, Jennifer; Epstein, Eric; Loyola, Karin; Rauscher, Michael; Buchmann, Stephen

2014-01-01

The understanding of physiological and molecular processes underlying the sense of smell has made considerable progress during the past three decades, revealing the cascade of molecular steps that lead to the activation of olfactory receptor (OR) neurons. However, the mode of primary interaction of odorant molecules with the OR proteins within the sensory cells is still enigmatic. Two different concepts try to explain these interactions: the ‘odotope hypothesis’ suggests that OR proteins recognize structural aspects of the odorant molecule, whereas the ‘vibration hypothesis’ proposes that intra-molecular vibrations are the basis for the recognition of the odorant by the receptor protein. The vibration hypothesis predicts that OR proteins should be able to discriminate compounds containing deuterium from their common counterparts which contain hydrogen instead of deuterium. This study tests this prediction in honeybees (Apis mellifera) using the proboscis extension reflex learning in a differential conditioning paradigm. Rewarding one odour (e.g. a deuterated compound) with sucrose and not rewarding the respective analogue (e.g. hydrogen-based odorant) shows that honeybees readily learn to discriminate hydrogen-based odorants from their deuterated counterparts and supports the idea that intra-molecular vibrations may contribute to odour discrimination. PMID:24452031

Risk of abortion and stillbirth in cow-calf herds exposed to the oil and gas industry in Western Canada.

PubMed

Waldner, Cheryl L

2009-01-01

To investigate the associations between emissions from oil and gas field facilities and fetal survival, researchers followed more than 28,000 beef cows from the beginning of the breeding season through calving. They prospectively measured exposure to sulfur dioxide, hydrogen sulfide, and volatile organic compounds and linked them to the location of individual cattle; they used the density of oil and gas well sites surrounding each pasture as an alternate measure of exposure. The researchers measured the risks of abortion and stillbirth in 203 cow-calf herds for the 2002 calving season, as well as animal and herd-management factors known or suspected to affect these parameters. Using mixed models to adjust for clustering by herd and after accounting for other known risk factors, they examined the associations between exposure to sulfur dioxide, volatile organic compounds measured as benzene and toluene, hydrogen sulfide, and well-site density, and the risks of abortion and stillbirth. There was no evidence across the measured range of exposures that emissions of sulfur dioxide, hydrogen sulfide, volatile organic compounds measured as benzene or toluene, or well-site density increased the risk of either abortion or stillbirth in these beef herds.

Zirconium-nickel crystals—hydrogen accumulators: Dissolution and penetration of hydrogen atoms in alloys

NASA Astrophysics Data System (ADS)

Matysina, Z. A.; Zaginaichenko, S. Yu.; Shchur, D. V.; Gabdullin, M. T.; Kamenetskaya, E. A.

2016-07-01

The calculation of the free energy, thermodynamic equilibrium equations, and kinetic equations of the intermetallic compound Zr2NiH x has been carried out based on molecular-kinetic concepts. The equilibrium hydrogen concentration depending on the temperature, pressure, and energy parameters has been calculated. The absorption-desorption of hydrogen has been studied, and the possibility of the realization of the hysteresis effect has been revealed. The kinetics of the dissolution and permeability of hydrogen is considered, the time dependence of these values has been found, and conditions for the extremum character of their time dependence have been determined. Relaxation times of the dissolution and permeability of hydrogen into the alloy have been calculated. The calculation results are compared with the experimental data available in the literature.

Crystal structures of three indole derivatives: 3-ethnyl-2-methyl-1-phenyl­sulfonyl-1H-indole, 4-phenyl­sulfonyl-3H,4H-cyclo­penta­[b]indol-1(2H)-one and 1-{2-[(E)-2-(5-chloro-2-nitro­phen­yl)ethen­yl]-1-phenyl­sulfonyl-1H-indol-3-yl}ethan-1-one chloro­form monosolvate

PubMed Central

Gopinath, S.; Sethusankar, K.; Ramalingam, Bose Muthu; Mohanakrishnan, Arasambattu K.

2015-01-01

The title compounds, C17H13NO2S, (I), C17H13NO3S, (II), and C24H17ClN2O5S·CHCl3, (III), are indole derivatives. Compounds (I) and (II) crystalize with two independent mol­ecules in the asymmetric unit. The indole ring systems in all three structures deviate only slightly from planarity, with dihedral angles between the planes of the pyrrole and benzene rings spanning the tight range 0.20 (9)–1.65 (9)°. These indole ring systems, in turn, are almost orthogonal to the phenyl­sulfonyl rings [range of dihedral angles between mean planes = 77.21 (8)–89.26 (8)°]. In the three compounds, the mol­ecular structure is stabilized by intra­molecular C—H⋯O hydrogen bonds, generating S(6) ring motifs with the sulfone O atom. In compounds (I) and (II), the two independent mol­ecules are linked by C—H⋯O hydrogen bonds and C—H⋯π inter­actions, while in compound (III), the mol­ecules are linked by C—H⋯O hydrogen bonds, generating R 2 2(22) inversion dimers. PMID:26396842

Dicobalt-μ-oxo polyoxometalate compound, [(α(2)-P2W17O61Co)2O](14-): a potent species for water oxidation, C-H bond activation, and oxygen transfer.

PubMed

Barats-Damatov, Delina; Shimon, Linda J W; Weiner, Lev; Schreiber, Roy E; Jiménez-Lozano, Pablo; Poblet, Josep M; de Graaf, Coen; Neumann, Ronny

2014-02-03

High-valent oxo compounds of transition metals are often implicated as active species in oxygenation of hydrocarbons through carbon-hydrogen bond activation or oxygen transfer and also in water oxidation. Recently, several examples of cobalt-catalyzed water oxidation have been reported, and cobalt(IV) species have been suggested as active intermediates. A reactive species, formally a dicobalt(IV)-μ-oxo polyoxometalate compound [(α2-P2W17O61Co)2O](14-), [(POMCo)2O], has now been isolated and characterized by the oxidation of a monomeric [α2-P2W17O61Co(II)(H2O)](8-), [POMCo(II)H2O], with ozone in water. The crystal structure shows a nearly linear Co-O-Co moiety with a Co-O bond length of ∼1.77 Å. In aqueous solution [(POMCo)2O] was identified by (31)P NMR, Raman, and UV-vis spectroscopy. Reactivity studies showed that [(POMCo)2O]2O] is an active compound for the oxidation of H2O to O2, direct oxygen transfer to water-soluble sulfoxides and phosphines, indirect epoxidation of alkenes via a Mn porphyrin, and the selective oxidation of alcohols by carbon-hydrogen bond activation. The latter appears to occur via a hydrogen atom transfer mechanism. Density functional and CASSCF calculations strongly indicate that the electronic structure of [(POMCo)2O]2O] is best defined as a compound having two cobalt(III) atoms with two oxidized oxygen atoms.

Joint adsorption of light hydrogen by CuO and 5A molecular sieves

NASA Astrophysics Data System (ADS)

Wang, J.; Zhan, Y.; Wang, W.; Wang, R. S.

2018-03-01

H2 is the primary cause of the deteriorating vacuum degree of high-vacuum multilayer insulation tank (HVMLIT). At present, the precious metal PdO is used to adsorb H2 and maintain the high vacuum of HVMLIT. In this study, CA, a compound hydrogen adsorbent integrated with the cheap metal CuO and 5A molecular sieves, is adopted to jointly adsorb light hydrogen in HVMLIT. This work also investigates the adsorption characteristics and mechanisms of CA.

Oxidation of hydrogen halides to elemental halogens with catalytic molten salt mixtures

DOEpatents

Rohrmann, Charles A.

1978-01-01

A process for oxidizing hydrogen halides by means of a catalytically active molten salt is disclosed. The subject hydrogen halide is contacted with a molten salt containing an oxygen compound of vanadium and alkali metal sulfates and pyrosulfates to produce an effluent gas stream rich in the elemental halogen. The reduced vanadium which remains after this contacting is regenerated to the active higher valence state by contacting the spent molten salt with a stream of oxygen-bearing gas.

Influence of dispersity on the activity, selectivity, and stability of Raney-Nickel catalyst during the hydrogenation of 1,4-butynediol into 1,4-butanediol

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

Rusina, S.V.; Litvin, E.F.; Kheifets, V.I.

Raney-nickel catalysts are widely used in the hydrogenation of 1,4-butynediol into 1,4-butanediol, an important intermediate for the preparation of thermostable resins, plasticizers, pharmaceutical preparations, and other compounds. The authors carried out the investigation of the influence of the dispersity of the Raney-nickel catalysts on their activity, selectivity, and stability in the hydrogenation reaction of 1,4-butynediol into 1,4-butanediol.

Evaluation of a Diffusion/Trapping Model for Hydrogen Ingress in High-Strength Alloys

DTIC Science & Technology

1990-11-14

Potential traps are the intermetallic compounds, Ni3Mo and possibly Ni3 Ti or FeTi, precipitated during age hardening of the maraging steel .23 The energy of...1972); Ref 105 in "The Stress Corrosion and Hydrogen Embrittlement Behavior of Maraging Steels ," Proceedings of the Conference on the Stress Corrosion ...718, 18Ni Maraging Steel Hydrogen Trapping, Incoloy 925, Titanium, Trapping Model 19. ABSTRACT (Continue on reverse if necessary and ientify by block

Metal-Element Compounds of Titanium, Zirconium, and Hafnium as Pyrotechnic Fuels

DTIC Science & Technology

2015-05-04

including ceramic materials in this role has been far less common. Following the development of boron carbide-based pyrotechnics in our laboratories, we...ameliorate these problems. Commercially available group 4 compounds containing hydrogen, boron , carbon, nitrogen, silicon, and phosphorus were obtained for...predicted behavior suggests that these compounds may be useful for a variety of pyrotechnic applications. 1. INTRODUCTION The recent use of boron

Evaluation of the separation characteristics of application-specific (volatile organic compounds) open-tubular columns for gas chromatography.

PubMed

Poole, Colin F; Qian, Jing; Kiridena, Waruna; Dekay, Colleen; Koziol, Wladyslaw W

2006-11-17

The solvation parameter model is used to characterize the separation characteristics of two application-specific open-tubular columns (Rtx-Volatiles and Rtx-VGC) and a general purpose column for the separation of volatile organic compounds (DB-WAXetr) at five equally spaced temperatures over the range 60-140 degrees C. System constant differences and retention factor correlation plots are then used to determine selectivity differences between the above columns and their closest neighbors in a large database of system constants and retention factors for forty-four open-tubular columns. The Rtx-Volatiles column is shown to have separation characteristics predicted for a poly(dimethyldiphenylsiloxane) stationary phase containing about 16% diphenylsiloxane monomer. The Rtx-VGC column has separation properties similar to the poly(cyanopropylphenyldimethylsiloxane) stationary phase containing 14% cyanopropylphenylsiloxane monomer DB-1701 for non-polar and dipolar/polarizable compounds but significantly different characteristics for the separation of hydrogen-bond acids. For all practical purposes the DB-WAXetr column is shown to be selectivity equivalent to poly(ethylene glycol) columns prepared using different chemistries for bonding and immobilizing the stationary phase. Principal component analysis and cluster analysis are then used to classify the system constants for the above columns and a sub-database of eleven open-tubular columns (DB-1, HP-5, DB-VRX, Rtx-20, DB-35, Rtx-50, Rtx-65, DB-1301, DB-1701, DB-200, and DB-624) commonly used for the separation of volatile organic compounds. A rationale basis for column selection based on differences in intermolecular interactions is presented as an aid to method development for the separation of volatile organic compounds.

Is it really organic?--multi-isotopic analysis as a tool to discriminate between organic and conventional plants.

PubMed

Laursen, K H; Mihailova, A; Kelly, S D; Epov, V N; Bérail, S; Schjoerring, J K; Donard, O F X; Larsen, E H; Pedentchouk, N; Marca-Bell, A D; Halekoh, U; Olesen, J E; Husted, S

2013-12-01

Novel procedures for analytical authentication of organic plant products are urgently needed. Here we present the first study encompassing stable isotopes of hydrogen, carbon, nitrogen, oxygen, magnesium and sulphur as well as compound-specific nitrogen and oxygen isotope analysis of nitrate for discrimination of organically and conventionally grown plants. The study was based on wheat, barley, faba bean and potato produced in rigorously controlled long-term field trials comprising 144 experimental plots. Nitrogen isotope analysis revealed the use of animal manure, but was unable to discriminate between plants that were fertilised with synthetic nitrogen fertilisers or green manures from atmospheric nitrogen fixing legumes. This limitation was bypassed using oxygen isotope analysis of nitrate in potato tubers, while hydrogen isotope analysis allowed complete discrimination of organic and conventional wheat and barley grains. It is concluded, that multi-isotopic analysis has the potential to disclose fraudulent substitutions of organic with conventionally cultivated plants. Copyright © 2013 Elsevier Ltd. All rights reserved.

40 CFR 60.704 - Test methods and procedures.

Code of Federal Regulations, 2013 CFR

2013-07-01

... (CONTINUED) STANDARDS OF PERFORMANCE FOR NEW STATIONARY SOURCES Standards of Performance for Volatile Organic Compound Emissions From Synthetic Organic Chemical Manufacturing Industry (SOCMI) Reactor Processes § 60... compound j in ppm, as measured for organics by Method 18 and measured for hydrogen and carbon monoxide by...

40 CFR 60.704 - Test methods and procedures.

Code of Federal Regulations, 2014 CFR

2014-07-01

... (CONTINUED) STANDARDS OF PERFORMANCE FOR NEW STATIONARY SOURCES Standards of Performance for Volatile Organic Compound Emissions From Synthetic Organic Chemical Manufacturing Industry (SOCMI) Reactor Processes § 60... basis of compound j in ppm, as measured for organics by Method 18 and measured for hydrogen and carbon...

Hydrogen halides at Comet 67P/Churyumov-Gerasimenko as detected by ROSINA-DFMS

NASA Astrophysics Data System (ADS)

Dhooghe, Frederik

2017-04-01

The Rosetta spacecraft has been studying the coma of comet 67P/Churyumov-Gerasimenko (67P/C-G) in-situ from the comet encounter in August 2014 up to end of mission in September 2016. The Rosetta Orbiter Spectrometer for Ion and Neutral Analysis (ROSINA) contains a double focussing mass spectrometer (DFMS) with a mass range 13-140 u/e. It is optimized for high mass resolution and large dynamic range for the chemical and isotopic characterization of the volatiles in the coma. Since comets retained information about the physical and chemical conditions of the protoplanetary disk from which they formed, they may provide insights into the halogen chemistry in the early Solar System. We have studied the halogen-bearing compounds in the coma with DFMS on 67P/C-G's inbound journey during four periods, as the gas production increased towards perihelion and as the comet's subsolar latitude moved from the northern to the southern hemisphere: (A) when Rosetta was close to the comet, during 1-31/10/2014, at 3.0-3.3 AU, (B) during the close flybys on 14/2/2015 and on 28/3/2015 at 2.3 AU and 2.0 AU, (C) post-equinox between 10/5/2015 and 1/6/2015, at 1.5-1.7 AU, and (D) around perihelion between 9/7/2015 and 31/8/2015, at 1.24-1.31 AU. The main halogen-bearing compounds in the comet atmosphere were found to be the hydrogen halides HF (hydrogen fluoride), HCl (hydrogen chloride) and HBr (hydrogen bromide). HF and HCl could be observed during all four periods, while hydrogen bromide could, due to its low abundance, only be detected during period A, when Rosetta was close to the comet. An increase in the halogen-to-oxygen ratio as a function of distance was observed which suggests a distributed source for HF and HCl, probably through progressive release of these compounds from grains. This contribution will address the abundance and variability of the hydrogen halides in the coma as well as the cometary isotopic ratios for 37Cl/35Cl and 81Br/79Br.

A novel compound inhibits rHDL assembly and blocks nascent HDL biogenesis downstream of apoAI binding to ABCA1 expressing cells

PubMed Central

Lyssenko, Nicholas N.; Brubaker, Gregory; Smith, Bradley D.; Smith, Jonathan D.

2011-01-01

Objective Nascent high-density lipoprotein (HDL) particles form from cellular lipids and extracellular lipid-free apolipoprotein AI (apoAI) in a process mediated by ATP-binding cassette transporter A1 (ABCA1). We have sought out compounds that inhibit nascent HDL biogenesis without affecting ABCA1 activity. Methods and Results Reconstituted HDL (rHDL) formation and cellular cholesterol efflux assays were used to show that two compounds that bond via hydrogen with phospholipids inhibit rHDL and nascent HDL production. In rHDL formation assays, the inhibitory effect of compound 1 (methyl 3α-acetoxy-7α,12α-di[(phenylaminocarbonyl)amino]-5β-cholan-24-oate), the more active of the two, depended on its ability to associate with phospholipids. In cell assays, compound 1 suppressed ABCA1-mediated cholesterol efflux to apoAI, the 18A peptide, and taurocholate with high specificity, without affecting ABCA1-independent cellular cholesterol efflux to HDL and endocytosis of acetylated low-density lipoprotein (AcLDL) and transferrin. Furthermore, compound 1 did not affect ABCA1 activity adversely, as ABCA1-mediated shedding of microparticles proceeded unabated and apoAI binding to ABCA1-expressing cells increased in its presence. Conclusions The inhibitory effects of compound 1 support a three-step model of nascent HDL biogenesis: plasma membrane remodeling by ABCA1, apoAI binding to ABCA1, and lipoprotein particle assembly. The compound inhibits the final step, causing accumulation of apoAI in ABCA1-expressing cells. PMID:21836073

Single crystal, vibrational and computational studies of Theophylline (a bronchodilator drug) and its chloride salt

NASA Astrophysics Data System (ADS)

Mary Novena, L.; Suresh Kumar, S.; Athimoolam, S.; Saminathan, K.; Sridhar, B.

2017-04-01

The crystal structure of Theophylline (TH) and Theophyillinium chloride monohydrate (THC) and its complete molecular structure analysis on theoretical and experimental methods is reported here. The hydrogen bonding studies were carried out as a special note of the present work. The electron density analyses of the compounds were also analyzed in view of the intermolecular interactions. Moreover, it is an ever first quantum chemical report of this drug (TH) and its chloride salt. In TH crystal, the water molecule connects the Theophylline molecules through Osbnd H⋯N hydrogen bond forming discrete D22(7) motif and dimeric ring R22(10) motif through Nsbnd H⋯O hydrogen bond. In THC, the two classical (Nsbnd H⋯O, Nsbnd H⋯Cl) and one non-classical (Csbnd H⋯O) hydrogen bonds produce two pentameric chain C55 (16) and C55(17) motifs. These two chain motifs are interconnected by Osbnd H⋯O hydrogen bond and cross linked by Nsbnd H⋯Cl and Osbnd H⋯Cl hydrogen bonds to produce octametric ring R88(27) and R88(28) motifs. The solubility test is carried out to enhance the drug solubility and the therapeutic effectiveness of the drug. Experimentally obtained vibrational wavenumbers are compared with the spectra obtained theoretically for both the compound. The strong intensity bands and the shifting of bands due to intermolecular hydrogen bonds are also investigated. The Mulliken atomic charges, HOMO-LUMO and thermodynamic properties are calculated using Density Functional Theory (DFT) and Hartree-Fock Theory (HF) using 6-311++G(d,p) basis set.

Modeling interactions between a β-O-4 type lignin model compound and 1-allyl-3-methylimidazolium chloride ionic liquid.

PubMed

Zhu, Youtao; Yan, Jing; Liu, Chengbu; Zhang, Dongju

2017-08-01

Aiming at understanding the molecular mechanism of the lignin dissolution in imidazolium-based ionic liquids (ILs), this work presents a combined quantum chemistry (QC) calculation and molecular dynamics (MD) simulation study on the interaction of the lignin model compound, veratrylglycerol-β-guaiacyl ether (VG) with 1-allyl-3-methylimidazolium chloride ([Amim]Cl). The monomer of VG is shown to feature a strong intramolecular hydrogen bond, and its dimer is indicated to present important π-π stacking and intermolecular hydrogen bonding interactions. The interactions of both the cation and anion of [Amim]Cl with VG are shown to be stronger than that between the two monomers, indicating that [Amim]Cl is capable of dissolving lignin. While Cl - anion forms a hydrogen-bonded complex with VG, the imidazolium cation interacts with VG via both the π-π stacking and intermolecular hydrogen bonding. The calculated interaction energies between VG and the IL or its components (the cation, anion, and ion pair) indicate the anion plays a more important role than the cation for the dissolution of lignin in the IL. Theoretical results provide help for understanding the molecular mechanism of lignin dissolution in imidazolium-based IL. The theoretical calculations on the interaction between the lignin model compound and [Amim]Cl ionic liquid indicate that the anion of [Amim]Cl plays a more important role for lignin dissolution although the cation also makes a substantial contribution. © 2017 Wiley Periodicals, Inc.

Clean hydrogen generation through the electrocatalytic oxidation of ethanol in a Proton Exchange Membrane Electrolysis Cell (PEMEC): Effect of the nature and structure of the catalytic anode

NASA Astrophysics Data System (ADS)

Lamy, Claude; Jaubert, Thomas; Baranton, Stève; Coutanceau, Christophe

2014-01-01

The electrocatalytic oxidation of ethanol was investigated in a Proton Exchange Membrane Electrolysis Cell (PEMEC) working at low temperature (20°C) on several Pt-based catalysts (Pt/C, PtSn/C, PtSnRu/C) in order to produce very clean hydrogen by electrolysis of a biomass compound. The electrocatalytic activity was determined by cyclic voltammetry and the rate of hydrogen evolution was measured for each catalyst at different current densities. The cell voltages UEtOH were recorded as a function of time for each current density. At 100 mA cm-2, i.e. 0.5 A with the 5 cm2 surface area PEMEC used, the cell voltage did not exceed 0.9 V for an evolution rate of about 220 cm3 of hydrogen per hour and the electrical energy consumed was less than 2.3 kWh (Nm3)-1, i.e. less than one half of the energy needed for water electrolysis (4.7 kWh (Nm3)-1 at UH2O = 2 V). This result is valid for the decomposition of any organic compound, particularly those originated from biomass resource, provided that their electro-oxidation rate is sufficient (>100 mA cm-2) at a relatively low cell voltage (Ucell < 1 V) which necessitates the development of efficient electrocatalysts for the electrochemical decomposition of this compound.

Implementation of an ADME enabling selection and visualization tool for drug discovery.

PubMed

Stoner, Chad L; Gifford, Eric; Stankovic, Charles; Lepsy, Christopher S; Brodfuehrer, Joanne; Prasad, J V N Vara; Surendran, Narayanan

2004-05-01

The pharmaceutical industry has large investments in compound library enrichment, high throughput biological screening, and biopharmaceutical (ADME) screening. As the number of compounds submitted for in vitro ADME screens increases, data analysis, interpretation, and reporting will become rate limiting in providing ADME-structure-activity relationship information to guide the synthetic strategy for chemical series. To meet these challenges, a software tool was developed and implemented that enables scientists to explore in vitro and in silico ADME and chemistry data in a multidimensional framework. The present work integrates physicochemical and ADME data, encompassing results for Caco-2 permeability, human liver microsomal half-life, rat liver microsomal half-life, kinetic solubility, measured log P, rule of 5 descriptors (molecular weight, hydrogen bond acceptors, hydrogen bond donors, calculated log P), polar surface area, chemical stability, and CYP450 3A4 inhibition. To facilitate interpretation of this data, a semicustomized software solution using Spotfire was designed that allows for multidimensional data analysis and visualization. The solution also enables simultaneous viewing and export of chemical structures with the corresponding ADME properties, enabling a more facile analysis of ADME-structure-activity relationship. In vitro and in silico ADME data were generated for 358 compounds from a series of human immunodeficiency virus protease inhibitors, resulting in a data set of 5370 experimental values which were subsequently analyzed and visualized using the customized Spotfire application. Implementation of this analysis and visualization tool has accelerated the selection of molecules for further development based on optimum ADME characteristics, and provided medicinal chemistry with specific, data driven structural recommendations for improvements in the ADME profile. Copyright 2004 Wiley-Liss, Inc. and the American Pharmacists Association J Pharm Sci 93: 1131-1141, 2004

Insights into the complex formed by matrix metalloproteinase-2 and alloxan inhibitors: molecular dynamics simulations and free energy calculations.

PubMed

Giangreco, Ilenia; Lattanzi, Gianluca; Nicolotti, Orazio; Catto, Marco; Laghezza, Antonio; Leonetti, Francesco; Stefanachi, Angela; Carotti, Angelo

2011-01-01

Matrix metalloproteinases (MMP) are well-known biological targets implicated in tumour progression, homeostatic regulation, innate immunity, impaired delivery of pro-apoptotic ligands, and the release and cleavage of cell-surface receptors. Hence, the development of potent and selective inhibitors targeting these enzymes continues to be eagerly sought. In this paper, a number of alloxan-based compounds, initially conceived to bias other therapeutically relevant enzymes, were rationally modified and successfully repurposed to inhibit MMP-2 (also named gelatinase A) in the nanomolar range. Importantly, the alloxan core makes its debut as zinc binding group since it ensures a stable tetrahedral coordination of the catalytic zinc ion in concert with the three histidines of the HExxHxxGxxH metzincin signature motif, further stabilized by a hydrogen bond with the glutamate residue belonging to the same motif. The molecular decoration of the alloxan core with a biphenyl privileged structure allowed to sample the deep S(1)' specificity pocket of MMP-2 and to relate the high affinity towards this enzyme with the chance of forming a hydrogen bond network with the backbone of Leu116 and Asn147 and the side chains of Tyr144, Thr145 and Arg149 at the bottom of the pocket. The effect of even slight structural changes in determining the interaction at the S(1)' subsite of MMP-2 as well as the nature and strength of the binding is elucidated via molecular dynamics simulations and free energy calculations. Among the herein presented compounds, the highest affinity (pIC(50) = 7.06) is found for BAM, a compound exhibiting also selectivity (>20) towards MMP-2, as compared to MMP-9, the other member of the gelatinases.

Influence of Various Phenolic Compounds on Properties of Gelatin Film Prepared from Horse Mackerel Trachurus japonicus Scales.

PubMed

Le, Thuy; Maki, Hiroki; Okazaki, Emiko; Osako, Kazufumi; Takahashi, Kigen

2018-06-15

Influence of various phenolic compounds on physical properties and antioxidant activity of gelatin film from horse mackerel Trachurus japonicus scales was investigated. Tensile strength (TS) of the film was enhanced whereas elongation at break was declined by adding 1% to 5% phenolic compounds. Rutin was the most effective to improve the TS compared to the other tested phenolic compounds including ferulic acid, caffeic acid, gallic acid, and catechin. Gelatin films with the phenolic compounds showed the excellent UV barrier properties. FTIR spectra exhibited that wavenumber of amide-A band of films decreased with formation of hydrogen bonding between amino groups of gelatin and hydroxyl groups of the phenolic compounds. Gelatin film incorporated with rutin which has the largest number of hydroxyl groups among the tested compounds demonstrated the lowest wavenumber for the amide-A peak. It is indicated that hydroxyl groups contained in the phenolic compounds contribute to formation of hydrogen bonds involved in improvement of the mechanical properties of the films. The incorporation of the phenolic compounds with gelatin films also led to the increasing of total phenolic contents and DPPH radical scavenging activities. Thus, it is concluded that phenolic compounds can promote the quality of gelatin film. Properties of gelatin film derived from horse mackerel scales can be improved by adding of phenolic compounds. Phenolic compounds containing a large number of hydroxyl groups should be selected to enhance physical properties of the gelatin film. A biodegradable film prepared from horse mackerel gelatin incorporated with phenolic compounds, which has good physical properties and antioxidant properties, can solve environmental problems caused by synthetic plastic materials. © 2018 Institute of Food Technologists®.

Methyl (4-bromo-benzene-sulfonamido)acetate.

PubMed

Arshad, Muhammad Nadeem; Tahir, M Nawaz; Khan, Islam Ullah; Ahmad, Ejaz; Shafiq, Muhammad

2008-11-20

The title compound, C(9)H(10)BrNO(4)S, is an inter-mediate for the formation of benzothia-zines. In the crystal structure, inter-molecular N-H⋯O hydrogen bonds link the mol-ecules, forming R(2) (2)(10) ring motifs, which are linked into a two-dimensional polymeric sheet through inter-molecular C-H⋯O hydrogen bonds.

The Determination of Hydrogen Sulfide in Stack Gases, Iodometric Titration After Sulfite Removal.

ERIC Educational Resources Information Center

Robles, E. G.

The determination of hydrogen sulfide in effluents from coal-fired furnaces and incinerators is complicated by the presence of sulfur oxides (which form acids). Organic compounds also may interfere with or prevent the formation of the cadmium sulfide precipitate or give false positive results because of reaction with iodine. The report presents a…

The abiotic degradation of soil organic matter to oxalic acid

NASA Astrophysics Data System (ADS)

Studenroth, Sabine; Huber, Stefan; Schöler, H. F.

2010-05-01

The abiotic degradation of soil organic matter to volatile organic compounds was studied intensely over the last years (Keppler et al., 2000; Huber et al., 2009). It was shown that soil organic matter is oxidised due to the presence of iron (III), hydrogen peroxide and chloride and thereby produces diverse alkyl halides, which are emitted into the atmosphere. The formation of polar halogenated compounds like chlorinated acetic acids which are relevant toxic environmental substances was also found in soils and sediments (Kilian et al., 2002). The investigation of the formation of other polar halogenated and non-halogenated compounds like diverse mono- and dicarboxylic acids is going to attain more and more importance. Due to its high acidity oxalic acid might have impacts on the environment e.g., nutrient leaching, plant diseases and negative influence on microbial growth. In this study, the abiotic formation of oxalic acid in soil is examined. For a better understanding of natural degradation processes mechanistic studies were conducted using the model compound catechol as representative for structural elements of the humic substances and its reaction with iron (III) and hydrogen peroxide. Iron is one of the most abundant elements on earth and hydrogen peroxide is produced by bacteria or through incomplete reduction of oxygen. To find suitable parameters for an optimal reaction and a qualitative and quantitative analysis method the following reaction parameters are varied: concentration of iron (III) and hydrogen peroxide, time dependence, pH-value and influence of chloride. Analysis of oxalic acid was performed employing an ion chromatograph equipped with a conductivity detector. The time dependent reaction shows a relatively fast formation of oxalic acid, the optimum yield is achieved after 60 minutes. Compared to the concentration of catechol an excess of hydrogen peroxide as well as a low concentration of iron (III) are required. In absence of chloride the degradation of catechol to oxalic acid delivers a maximum yield of approximately 60 %, whereas the presence of chloride reduces the formation of oxalic acid to 30 %. Chloride possibly induces further competing reactions of catechol leading to a lower concentration of oxalic acid. Freeze-dried soil samples have been tested for production of oxalic acid, where the rate of organic matter seems to play an important role for the formation. By adding iron (III) and/or hydrogen peroxide oxalic acid yields increase, which demonstrates the reaction of soil organic matter with iron (III) and hydrogen peroxide as expected. Thus the natural abiotic formation of oxalic acid is confirmed. The results of the soil measurements are similar to those obtained with catechol. Therefore, the newly gained insights with model compounds appear to be applicable to soil conditions and these findings increase our understanding of the degradation pathways of soil organic matter. Furthermore an overview of the rates of oxalic acid formation of a variety of soil samples is shown and discussed in the light of different soil parameter.

Students' Understanding of Molecular Structure and Properties of Organic Compounds.

ERIC Educational Resources Information Center

Schmidt, Hans-Jurgen

The purpose of this study was to investigate senior high school students' difficulties predicting the existence of hydrogen bridge bonds between organic molecules, investigate students' difficulties predicting the relative boiling points of simple organic compounds, and develop test questions that enable teachers to quickly get information about…

Methyl 3-amino-4-butanamido-5-methyl­benzoate

PubMed Central

Li, Xiang; Yuan, Lian-shan; Wang, Dan; Yao, Cheng

2008-01-01

The title compound, C13H18N2O3, is an inter­mediate in the synthesis of compounds with medicinial applications. The crystal structure is stabilized by inter­molecular N—H⋯O, C—H⋯N and C—H⋯O hydrogen bonds. PMID:21202582

Synthesis, Photophysical Characterization, and Gelation Studies of a Stilbene-Cholesterol Derivative

ERIC Educational Resources Information Center

Geiger, H. Christina; Geiger, David K.; Baldwin, Christine

2006-01-01

Organogels are low molar mass organic compounds with the ability to immobilize an incredible quantity of solvent and fibrous aggregation of these compounds formed by noncovalent interaction usually involves hydrogen bonding. For stilbene-cholesterol based gelators, the driving force for molecular aggregation are weak van der Waal interactions…

Probing hydrogen and halogen-oxo interactions in uranyl coordination polymers: a combined crystallographic and computational study

DOE PAGES

Carter, Korey P.; Kalaj, Mark; Kerridge, Andrew; ...

2018-01-01

Four uranyl compounds containing either benzoic acid ( 1 ), m -chlorobenzoic acid ( 2 ), m -bromobenzoic acid ( 3 ), or m -iodobenzoic acid ( 4 ) are described, and the latter two compounds are used to probe non-covalent interaction strengths via structural, vibrational, and computational means.

Investigation of Source of Irritant Gas Produced by PATRIOT Missile System Air Conditioners

DTIC Science & Technology

1986-03-31

is the mass fragment CF3 . It is a common fragment of perfluorinated hydrocarbons, and is found to be present in most of the compounds detected by...used would allow detection of the target par3meters acrolein, aromatics, a broad range of organic compounds ,. formaldehyde, and hydrogen cyanide...organic compounds were observed. Thus, aromatic organic compounds were not produced by or from any of the four new units tested. 4 1CZ 3) With the

Isothermal Decomposition of Hydrogen Peroxide Dihydrate

NASA Technical Reports Server (NTRS)

Loeffler, M. J.; Baragiola, R. A.

2011-01-01

We present a new method of growing pure solid hydrogen peroxide in an ultra high vacuum environment and apply it to determine thermal stability of the dihydrate compound that forms when water and hydrogen peroxide are mixed at low temperatures. Using infrared spectroscopy and thermogravimetric analysis, we quantified the isothermal decomposition of the metastable dihydrate at 151.6 K. This decomposition occurs by fractional distillation through the preferential sublimation of water, which leads to the formation of pure hydrogen peroxide. The results imply that in an astronomical environment where condensed mixtures of H2O2 and H2O are shielded from radiolytic decomposition and warmed to temperatures where sublimation is significant, highly concentrated or even pure hydrogen peroxide may form.

Impact of the hydrogen partial pressure on lactate degradation in a coculture of Desulfovibrio sp. G11 and Methanobrevibacter arboriphilus DH1.

PubMed

Junicke, H; Feldman, H; van Loosdrecht, M C M; Kleerebezem, R

2015-04-01

In this study, the impact of the hydrogen partial pressure on lactate degradation was investigated in a coculture of Desulfovibrio sp. G11 and Methanobrevibacter arboriphilus DH1. To impose a change of the hydrogen partial pressure, formate was added to the reactor. Hydrogen results from the bioconversion of formate besides lactate in the liquid phase. In the presence of a hydrogen-consuming methanogen, this approach allows for a better estimation of low dissolved hydrogen concentrations than under conditions where hydrogen is supplied externally from the gas phase, resulting in a more accurate determination of kinetic parameters. A change of the hydrogen partial pressure from 1,200 to 250 ppm resulted in a threefold increase of the biomass-specific lactate consumption rate. The 50 % inhibition constant of hydrogen on lactate degradation was determined as 0.692 ± 0.064 μM dissolved hydrogen (831 ± 77 ppm hydrogen in the gas phase). Moreover, for the first time, the maximum biomass-specific lactate consumption rate of Desulfovibrio sp. G11 (0.083 ± 0.006 mol-Lac/mol-XG11/h) and the affinity constant for hydrogen uptake of Methanobrevibacter arboriphilus DH1 (0.601 ± 0.022 μM dissolved hydrogen) were determined. Contrary to the widely established view that the biomass-specific growth rate of a methanogenic coculture is determined by the hydrogen-utilizing partner; here, it was found that the hydrogen-producing bacterium determined the biomass-specific growth rate of the coculture grown on lactate and formate.

Chiral self-discrimination of the enantiomers of alpha-phenylethylamine derivatives in proton NMR.

PubMed

Huang, Shao-Hua; Bai, Zheng-Wu; Feng, Ji-Wen

2009-05-01

Two types of chiral analytes, the urea and amide derivatives of alpha-phenylethylamine, were prepared. The effect of inter-molecular hydrogen-bonding interaction on self-discrimination of the enantiomers of analytes has been investigated using high-resolution (1)H NMR. It was found that the urea derivatives with double-hydrogen-bonding interaction exhibit not only the stronger hydrogen-bonding interaction but also better self-recognition abilities than the amide derivatives (except for one bearing two NO(2) groups). The present results suggest that double-hydrogen-bonding interaction promotes the self-discrimination ability of the chiral compounds. Copyright (c) 2009 John Wiley & Sons, Ltd.

Thermodynamic study on the role of hydrogen during the MOVPE growth of group III nitrides

NASA Astrophysics Data System (ADS)

Koukitu, Akinori; Taki, Tetsuya; Takahashi, Naoyuki; Seki, Hisashi

1999-02-01

The role of hydrogen during the MOVPE growth of group III nitrides is investigated from a thermodynamic point of view. The effect of hydrogen is reported for the driving force for the deposition of binary nitrides as functions of growth temperature and V/III ratio. The effect of hydrogen for the InGaN growth is discussed for the vapor-solid relationship, the formation of compositional inhomogeneity and input partial pressure of the group III elements. The difference between the growth reaction of the indium containing nitrides and that of other III-V compounds is also discussed.

Inhibitors of calling behavior of Plodia interpunctella

PubMed Central

Hirashima, Akinori; Shigeta, Yoko; Eiraku, Tomohiko; Kuwano, Eiichi

2003-01-01

Some octopamine agonists were found to suppress the calling behavior of the stored product Indian meal moth, Plodia interpunctella. Compounds were screened using a calling behavior bioassay using female P. interpunctella. Four active derivatives, with inhibitory activity at the nanomolar range, were identified in order of decreasing activity: 2-(1-phenylethylamino)-2-oxazoline > 2-(2-ethyl,6-methylanilino)oxazolidine > 2-(2-methyl benzylamino)-2-thiazoline > 2-(2,6-diethylanilino)thiazolidine. Three-dimensional pharmacophore hypotheses were built from a set of 15 compounds. Among the ten common-featured models generated by the program Catalyst/HipHop, a hypothesis including a hydrogen-bond acceptor lipid, a hydrophobic aromatic and two hydrophobic aliphatic features was considered to be essential for inhibitory activity in the calling behavior. Active compounds mapped well onto all the hydrogen-bond acceptor lipid, hydrophobic aromatic and hydrophobic aliphatic features of the hypothesis. On the other hand, less active compounds were shown not to achieve the energetically favorable conformation that is found in the active molecules in order to fit the 3D common-feature pharmacophore models. The present studies demonstrate that inhibition of calling behavior is via an octopamine receptor. Abbreviation: AII 2-(arylimino)imidazolidine AIO 2-(arylimino)oxazolidine AIT 2-(arylimino)thiazolidine CBO 2-(4-chlorobenzylamino)-2-(4-phenyl)oxazoline CDM chlordimeform Confs number of conformers DIP 2-(2,6-diethylphenylimino)piperidine Features/Confs total number of features divided by the number of conformers (summed over the entire family of conformers) HBA hydrogen-bond acceptor HBAl hydrogen-bond acceptor lipid HBD hydrogen-bond donor Hp hydrophobic HpAl hydrophobic aliphatic HpAr hydrophobic aromatic mp melting point MTO 2-(3-methyl benzylthio)-2-oxazoline NI negative ionizable NIO 2-(1-naphthylimino)oxazolidine OA octopamine ODA 2-phenyl-5,6-dihydro-4H-1,3,4-oxadiazine ODO 2-phenyl-5,6-dihydro-4H-1,3,4-oxadiazine-5(6H)-one PBAN pheromone biosynthesis activating neuropeptide PEO 2-(1-phenylethylamino)-2-oxazoline PI positive ionizable PIT 1-(2,6-dimethylphenyl)imidazolidine-2-thione RA ring aromatic SBO 2-(substituted benzylamino)-2-oxazoline SBT 2-(substituted benzylamino)-2-thiazoline STO 2-(substituted benzylthio)-2-oxazoline ZETA (Z,E)-9,12-tetradecadienyl acetate PMID:15841221

Catalytic hydrogenation of polyaromatic hydrocarbon (PAH) compounds in supercritical carbon dioxide over supported palladium.

PubMed

Yuan, Tao; Marshall, William D

2007-12-01

A series of supported palladium catalysts were evaluated for their ability to mediate the complete hydrogenation of polycyclic aromatic hydrocarbon (PAH) compounds. Benzo[a]pyrene (B[a]P) or phenanthrene (Phe) in hexane was merged with a hydrogen-carbon dioxide [5% (w/w) H(2)/CO(2)] stream and transferred to a flow through mini-reactor (capacity ca. 1 g) that was maintained at 90 degrees C under a back-pressure of 20.68 MPa. Effluent from the reactor trapped in hexane was monitored/quantified by gas chromatography-mass spectrometry. Catalyst formulations supported on iron powder, high density polyethylene (HDPE) or gamma-alumina were prepared and compared in terms of hydrogenation activity as measured by the quantity of substrate per unit time that could be perhydrogenated to toxicologically innocuous products. Both of the Pd preparations supported on gamma-alumina were more efficient than a commercial Pd(0) (5% w/w) on gamma-Al(2)O(3) formulation or preparations supported on HDPE or the iron powder. Bimetallic mixtures with Pd increased the hydrogenation activity when co-deposited with Cu or Ni but not with Ag or Co. However, increases in hydrogenation activity by increasing the loading of Pd (or bimetallic mixture) on this surface were limited. Despite using supercritical carbon dioxide (scCO(2)) to swell the surfaces of the polymer, the deposition of nanoparticles within the polyethylene formulation was appreciably less active than either the oxidic or the Fe(0) formulations.

Prediction of superconducting iron–bismuth intermetallic compounds at high pressure

PubMed Central

Amsler, Maximilian; Naghavi, S. Shahab

2017-01-01

The synthesis of materials in high-pressure experiments has recently attracted increasing attention, especially since the discovery of record breaking superconducting temperatures in the sulfur–hydrogen and other hydrogen-rich systems. Commonly, the initial precursor in a high pressure experiment contains constituent elements that are known to form compounds at ambient conditions, however the discovery of high-pressure phases in systems immiscible under ambient conditions poses an additional materials design challenge. We performed an extensive multi component ab initio structural search in the immiscible Fe–Bi system at high pressure and report on the surprising discovery of two stable compounds at pressures above ≈36 GPa, FeBi2 and FeBi3. According to our predictions, FeBi2 is a metal at the border of magnetism with a conventional electron–phonon mediated superconducting transition temperature of T c = 1.3 K at 40 GPa. PMID:28507678

Prediction of superconducting iron–bismuth intermetallic compounds at high pressure

DOE PAGES

Amsler, Maximilian; Naghavi, S. Shahab; Wolverton, Chris

2016-12-07

The synthesis of materials in high-pressure experiments has recently attracted increasing attention, especially since the discovery of record breaking superconducting temperatures in the sulfur–hydrogen and other hydrogen-rich systems. Commonly, the initial precursor in a high pressure experiment contains constituent elements that are known to form compounds at ambient conditions, however the discovery of high-pressure phases in systems immiscible under ambient conditions poses an additional materials design challenge. We performed an extensive multi component ab initio structural search in the immiscible Fe–Bi system at high pressure and report on the surprising discovery of two stable compounds at pressures above ≈36 GPa,more » FeBi 2 and FeBi 3. According to our predictions, FeBi 2 is a metal at the border of magnetism with a conventional electron–phonon mediated superconducting transition temperature of T c = 1.3 K at 40 GPa.« less

anticonvulsant and toxicity evaluation of newer 4H-benzo[1,4]oxazin-3-ones: The effect of two hydrogen bonding domains.

PubMed

Siddiqui, Nadeem; Ali, Ruhi; Arshad, M Faiz; Ahsan, Waquar; Ahmed, Sharique; Alam, M Shamsher

2010-11-01

A series of (Z)-2-(substituted aryl)-N-(3-oxo-4-(substituted carbamothioyl)-3,4-dihydro-2H-benzo[b][1,4]oxazin-7-yl) hydrazine carboxamides (6a-r) was synthesized using 2-amino-5-nitrophenol as a starting material. All the synthesized compounds possessed two hydrogen-bonding domains and their effect on the activity was studied thereof. The anticonvulsant activity was assessed by the maximal electroshock test (MES), subcutaneous pentylenetetrazole test (scPTZ) and intraperitoneal thiosemicarbazide test (ipTSC). Compounds (6b, 6h, 6i, and 6p) were found to be the most potent of the series as they showed 83-100% protection in the MES test. They also displayed considerable activity in the chemically induced seizure tests. Most of the tested compounds were devoid of the neurotoxic and hepatotoxic effects.

Sweetness prediction of natural compounds.

PubMed

Chéron, Jean-Baptiste; Casciuc, Iuri; Golebiowski, Jérôme; Antonczak, Serge; Fiorucci, Sébastien

2017-04-15

Based on the most exhaustive database of sweeteners with known sweetness values, a new quantitative structure-activity relationship model for sweetness prediction has been set up. Analysis of the physico-chemical properties of sweeteners in the database indicates that the structure of most potent sweeteners combines a hydrophobic scaffold functionalized by a limited number of hydrogen bond sites (less than 4 hydrogen bond donors and 10 acceptors), with a moderate molecular weight ranging from 350 to 450g·mol -1 . Prediction of sweetness, bitterness and toxicity properties of the largest database of natural compounds have been performed. In silico screening reveals that the majority of the predicted natural intense sweeteners comprise saponin or stevioside scaffolds. The model highlights that their sweetness potency is comparable to known natural sweeteners. The identified compounds provide a rational basis to initiate the design and chemosensory analysis of new low-calorie sweeteners. Copyright © 2016 Elsevier Ltd. All rights reserved.

Single Crystal X-ray Study of 6-Phenyl-4-( p-tolyl)pyridin-2(1 H)-one

NASA Astrophysics Data System (ADS)

Khajuria, Rajni; Sharma, Suresh; Kapoor, Kamal K.; Gupta, Vivek K.

2017-12-01

The title compound 6-phenyl-4-( p-tolyl)pyridin-2(1 H)-one was synthesized via one-pot, three component reaction of ( E)-1-phenyl-3-( p-tolyl)-2-propen-1-one, ethyl 2-nitroacetate and ammonium acetate in refluxing ethanol, as a shiny green crystalline solid in 83% yield. Its structure was characterized by spectral studies and unambiguously corroborated by X-ray diffraction crystallography. The crystals of title compound are monoclinic, sp. gr. P21/ n, a = 11.8346(7) Å, b = 13.4413(9) Å, c = 17.7626(10) Å, β = 99.479(5)°, and Z = 8. All the rings in molecule of the title compound are planar. Hydrogen interactions play significant role in stabilizing the crystal structure and the supramolecular aggregate of molecules is facilitated by strong N-H···O and C-H···O type of hydrogen interactions.

Deuterium separation by infrared-induced addition reaction

DOEpatents

Marling, John B.

1977-01-01

A method for deuterium enrichment by the infrared-induced addition reaction of a deuterium halide with an unsaturated aliphatic compound. A gaseous mixture of a hydrogen halide feedstock and an unsaturated aliphatic compound, particularly an olefin, is irradiated to selectively vibrationally excite the deuterium halide contained therein. The excited deuterium halide preferentially reacts with the unsaturated aliphatic compound to produce a deuterated addition product which is removed from the reaction mixture.

Structure-Based Virtual Screening for Dopamine D2 Receptor Ligands as Potential Antipsychotics.

PubMed

Kaczor, Agnieszka A; Silva, Andrea G; Loza, María I; Kolb, Peter; Castro, Marián; Poso, Antti

2016-04-05

Structure-based virtual screening using a D2 receptor homology model was performed to identify dopamine D2 receptor ligands as potential antipsychotics. From screening a library of 6.5 million compounds, 21 were selected and were subjected to experimental validation. From these 21 compounds tested, ten D2 ligands were identified (47.6% success rate, among them D2 receptor antagonists, as expected) that have additional affinity for other receptors tested, in particular 5-HT2A receptors. The affinity (Ki values) of the compounds ranged from 58 nm to about 24 μM. Similarity and fragment analysis indicated a significant degree of structural novelty among the identified compounds. We found one D2 receptor antagonist that did not have a protonatable nitrogen atom, which is a key structural element of the classical D2 pharmacophore model necessary for interaction with the conserved Asp(3.32) residue. This compound exhibited greater than 20-fold binding selectivity for the D2 receptor over the D3 receptor. We provide additional evidence that the amide hydrogen atom of this compound forms a hydrogen bond with Asp(3.32), as determined by tests of its derivatives that cannot maintain this interaction. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Development of a nickel/metal hydride battery (Ni/MH) system for EV application

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

Ikoma, M.; Hamada, S.; Morishita, N.

1994-12-31

In order to satisfy basic battery characteristics for electric vehicles (EV) such as specific energy, specific power and cycle life that are required for driving on urban streets, the authors have selected the valve-regulated lead acid battery as a conventional battery and the nickel/metal-hydride battery as an advanced battery, and have been studying their development in order to put them into practical use by 1998. Regarding the nickel/metal-hydride battery, excellent nickel positive electrode with high temperature charge efficiency accomplished with additives such as Ca compounds, and an exceedingly good hydrogen absorbing alloy negative electrode with high capacity and long cyclemore » life, achieved by adjustment of alloy composition, surface treatment, and control of binder and conductive additive have been developed to overcome difficulties in the scale-up of battery size. Modular batteries using this technology possess specific energy twice (70 Wh/kg) that of the lead-acid battery, and have superior specific power (160 Wh/kg) and cycle life. 5 refs.« less

Sulfur and Hydrogen Isotope Anomalies in Organic Compounds from the Murchison Meteorite

NASA Technical Reports Server (NTRS)

Cooper, G. W.; Thiemens, M. H.; Jackson, T.; Chang, Sherwood

1996-01-01

Isotopic measurements have been made on organic sulfur and phosphorus compounds recently discovered in the Murchison meteorite. Carbon, hydrogen and sulfur measurements were performed on individual members of the organic sulfur compounds, alkyl sulfonates; and carbon and hydrogen measurements were made on bulk alkyl phosphonates. Cooper and Chang reported the first carbon isotopic measurements of Murchison organic sulfonates, providing insight into the potential synthetic mechanisms of these and, possibly, other organic species. Hydrogen isotopic measurements of the sulforiates now reveal deuterium excesses ranging from +660 to +2730 %. The deuterium enrichments indicate formation of the hydrocarbon portion of these compounds in a low temperature astrophysical environment consistent with that of dense molecular clouds. Measurements of the sulfur isotopes provide further constraints on the origin and mechanism of formation of these organic molecules. Recently, there has been growing documentation of sulfur isotopic anomalies in meteoritic material. Thiemens and Jackson have shown that some bulk ureilites possess excess S-33 and Thiemens et al. have reported excess S-33 in an oldhamite separate from the Norton County meteorite. Rees and Thode reported a large S-33 excess in an Allende acid residue, however, attempts to verify this measurements have been unsuccessful, possibly due to the heterogeneous nature of the carrier phase. With the recognition that sulfur isotopes may reflect chemistry in the protosolar nebula or the precursor molecular cloud, identification of potential carriers is of considerable interest. In the present study, the stable isotopes of sulfur were measured in methane sulfonic acid extracted from the Murchison meteorite. The isotopic composition was found to be: (delta)S-33 = 2.48 %, (delta)S-34 = 2.49 % and (delta)S-36 = 6.76 %. Based upon analysis of more than 60 meteoritic and numerous terrestrial samples, the mass fractionation lines are defined by Delta-33 = (delta)S-33 -0.50(delta)S-34 and Delta-36 = (delta)s-36 - 1.97 (delta)S-34. From these relationships Delta-33 = 1.24 % and Delta-36 = 0.89 % are observed. These anomalies, particularly the Delta-33, lie well outside the range of analytical uncertainty. They are the largest observed in any meteoritic component and the first found in an organosulfur compound. As discussed by Thiemens and Jackson, due to it's position on the periodic chart, sulfur undergoes chemically induced mass independent isotopic fractionations as does oxygen. Experiments by Mauersberger et. al. show that in such processes, the magnitude of fractionation for the different isotopically substituted species varies with mass and angular momentum; thus, anomalies are expected for both S-33 and S-36, but not necessarily of the same magnitude. Laboratory experiments have also confirmed that chemically produced, mass independent fractionations are mediated by molecular symmetry factors. A chemical source of fractionation requires that the sulfur isotopic anomaly was established in the gas phase, probably in reactions involving symmetric CS2. The discovery of an anomalous sulfur isotopic composition in a specific molecule containing excess deuterium is an important advance in the understanding of the cosmochemistry of sulfur. This evidence suggests that methanesulfonic acid was synthesized by interstellar processes. Further measurements and details of possible synthesis and fractionation mechanisms will be presented.

Novel Polyfluorinated Compounds Identified Using High ...

EPA Pesticide Factsheets

Concern over persistence, bioaccumulation, and toxicity has led to international regulation and phase-outs of certain perfluorinated compounds and little is known about their replacement products. High resolution mass spectrometry was used to investigate the occurrence and identity of replacement fluorinated compounds in surface water and sediment of the Tennessee River near Decatur, Alabama. Analysis of legacy Per- and polyfluoroalkyl substances (PFASs) revealed a marked increase in concentrations downstream of manufacturing facilities, with the most abundant compounds being perfluorooctanesulfonate (PFOS), perfluorobutanesulfonate (PFBS), and perfluorooctanoic acid (PFOA) as high as 220 ng L–1, 160 ng L–1, and 120 ng L–1, respectively. A series of nine polyfluorinated carboxylic acids was discovered, each differing by CF2CH2. These acids are likely products or byproducts of a manufacturing process that uses 1,1-difluoroethene, which is registered to a manufacturing facility in the area. Two other predominant compounds discovered have structures consistent with perfluorobutanesulfonate and perfluoroheptanoic acid but have a single hydrogen substituted for a fluorine someplace in their structure. A polyfluoroalkyl sulfate with differing mixes of hydrogen and fluorine substitution was also observed. N-methyl perfluorobutane sulfonamidoacetic acid (MeFBSAA) was observed at high concentrations and several other perfluorobutane sulfonamido substances were pres

Pressurized entrained-flow pyrolysis of microalgae: Enhanced production of hydrogen and nitrogen-containing compounds.

PubMed

Maliutina, Kristina; Tahmasebi, Arash; Yu, Jianglong

2018-05-01

Pressurized entrained-flow pyrolysis of Chlorella vulgaris microalgae was investigated. The impact of pressure on the yield and composition of pyrolysis products were studied. The results showed that the concentration of H 2 in bio-gas increased sharply with increasing pyrolysis pressure, while those of CO, CO 2 , CH 4 , and C 2 H 6 were dramatically decreased. The concentration of H 2 reached 88.01 vol% in bio-gas at 900 °C and 4 MPa. Higher pressures promoted the hydrogen transfer to bio-gas. The bio-oils derived from pressurized pyrolysis were rich in nitrogen-containing compounds and PAHs. The highest concentration of nitrogen-containing compounds in bio-oil was achieved at 800 °C and 1 MPa. Increasing pyrolysis pressure promoted the formation of nitrogen-containing compounds such as indole, quinoline, isoquinoline and phenanthridine. Higher pyrolysis pressures led to increased sphericity, enhanced swelling, and higher carbon order of bio-chars. Pressurized pyrolysis of biomass has a great potential for poly-generation of H 2 , nitrogen containing compounds and bio-char. Copyright © 2018 Elsevier Ltd. All rights reserved.

Quantitative estimation of pesticide-likeness for agrochemical discovery.

PubMed

Avram, Sorin; Funar-Timofei, Simona; Borota, Ana; Chennamaneni, Sridhar Rao; Manchala, Anil Kumar; Muresan, Sorel

2014-12-01

The design of chemical libraries, an early step in agrochemical discovery programs, is frequently addressed by means of qualitative physicochemical and/or topological rule-based methods. The aim of this study is to develop quantitative estimates of herbicide- (QEH), insecticide- (QEI), fungicide- (QEF), and, finally, pesticide-likeness (QEP). In the assessment of these definitions, we relied on the concept of desirability functions. We found a simple function, shared by the three classes of pesticides, parameterized particularly, for six, easy to compute, independent and interpretable, molecular properties: molecular weight, logP, number of hydrogen bond acceptors, number of hydrogen bond donors, number of rotatable bounds and number of aromatic rings. Subsequently, we describe the scoring of each pesticide class by the corresponding quantitative estimate. In a comparative study, we assessed the performance of the scoring functions using extensive datasets of patented pesticides. The hereby-established quantitative assessment has the ability to rank compounds whether they fail well-established pesticide-likeness rules or not, and offer an efficient way to prioritize (class-specific) pesticides. These findings are valuable for the efficient estimation of pesticide-likeness of vast chemical libraries in the field of agrochemical discovery. Graphical AbstractQuantitative models for pesticide-likeness were derived using the concept of desirability functions parameterized for six, easy to compute, independent and interpretable, molecular properties: molecular weight, logP, number of hydrogen bond acceptors, number of hydrogen bond donors, number of rotatable bounds and number of aromatic rings.

Determination of atomic hydrogen in non-thermal hydrogen plasmas by means of molecular beam threshold ionization mass spectrometry.

PubMed

Wang, Wei-Guo; Xu, Yong; Yang, Xue-Feng; Wang, Wen-Chun; Zhu, Ai-Min

2005-01-01

Atomic hydrogen plays important roles in chemical vapor deposition of functional materials, plasma etching and new approaches to chemical synthesis of hydrogen-containing compounds. The present work reports experimental determinations of atomic hydrogen near the grounded electrode in medium-pressure dielectric barrier discharge hydrogen plasmas by means of molecular beam threshold ionization mass spectrometry (MB-TIMS). At certain discharge conditions (a.c. frequency of 24 kHz, 28 kV of peak-to-peak voltage), the measured hydrogen dissociation fraction is decreased from approximately 0.83% to approximately 0.14% as the hydrogen pressure increases from 2.0 to 14.0 Torr. A simulation method for extraction of the approximate electron beam energy distribution function in the mass spectrometer ionizer and a semi-quantitative approach to calibrate the mass discrimination effect caused by the supersonic beam formation and the mass spectrometer measurement are reported. Copyright 2005 John Wiley & Sons, Ltd.

The influence of hydrogen bonding on partition coefficients

NASA Astrophysics Data System (ADS)

Borges, Nádia Melo; Kenny, Peter W.; Montanari, Carlos A.; Prokopczyk, Igor M.; Ribeiro, Jean F. R.; Rocha, Josmar R.; Sartori, Geraldo Rodrigues

2017-02-01

This Perspective explores how consideration of hydrogen bonding can be used to both predict and better understand partition coefficients. It is shown how polarity of both compounds and substructures can be estimated from measured alkane/water partition coefficients. When polarity is defined in this manner, hydrogen bond donors are typically less polar than hydrogen bond acceptors. Analysis of alkane/water partition coefficients in conjunction with molecular electrostatic potential calculations suggests that aromatic chloro substituents may be less lipophilic than is generally believed and that some of the effect of chloro-substitution stems from making the aromatic π-cloud less available to hydrogen bond donors. Relationships between polarity and calculated hydrogen bond basicity are derived for aromatic nitrogen and carbonyl oxygen. Aligned hydrogen bond acceptors appear to present special challenges for prediction of alkane/water partition coefficients and this may reflect `frustration' of solvation resulting from overlapping hydration spheres. It is also shown how calculated hydrogen bond basicity can be used to model the effect of aromatic aza-substitution on octanol/water partition coefficients.

Crystal structures of 3,5-bis-[(E)-3-hy-droxy-benzyl-idene]-1-methyl-piperidin-4-one and 3,5-bis-[(E)-2-chloro-benzyl-idene]-1-methyl-piperidin-4-one.

PubMed

Eryanti, Yum; Zamri, Adel; Herlina, Tati; Supratman, Unang; Rosli, Mohd Mustaqim; Fun, Hoong-Kun

2015-12-01

The title compounds, C20H19NO3, (1), and C20H17Cl2NO, (2), are the 3-hy-droxy-benzyl-idene and 2-chloro-benzyl-idene derivatives, respectively, of curcumin [systematic name: (1E,6E)-1,7-bis-(4-hy-droxy-3-meth-oxy-phen-yl)-1,6-hepta-diene-3,5-dione]. The dihedral angles between the benzene rings in each compound are 21.07 (6)° for (1) and 13.4 (3)° for (2). In both compounds, the piperidinone rings adopt a sofa confirmation and the methyl group attached to the N atom is in an equatorial position. In the crystal of (1), two pairs of O-H⋯N and O-H⋯O hydrogen bonds link the mol-ecules, forming chains along [10-1]. The chains are linked via C-H⋯O hydrogen bonds, forming undulating sheets parallel to the ac plane. In the crystal of (2), mol-ecules are linked by weak C-H⋯Cl hydrogen bonds, forming chains along the [204] direction. The chains are linked along the a-axis direction by π-π inter-actions [inter-centroid distance = 3.779 (4) Å]. For compound (2), the crystal studied was a non-merohedral twin with the refined ratio of the twin components being 0.116 (6):0.886 (6).

POTENT INHIBITORS OF HUMAN ORGANIC ANION TRANSPORTERS 1 AND 3 FROM CLINICAL DRUG LIBRARIES: DISCOVERY AND MOLECULAR CHARACTERIZATION

PubMed Central

Duan, Peng; Li, Shanshan; Ai, Ni; Hu, Longqin; Welsh, William J.; You, Guofeng

2012-01-01

Transporter-mediated drug-drug interactions in the kidney dramatically influence the pharmacokinetics and other clinical effects of drugs. Human organic anion transporters 1 (hOAT1) and 3 (hOAT3) are the major transporters in the basolateral membrane of kidney proximal tubules, mediating the rate-limiting step in the elimination of a broad spectrum of drugs. In the present study, we screened two clinical drug libraries against hOAT1 and hOAT3. Of the 727 compounds screened, 92 compounds inhibited hOAT1 and 262 compounds inhibited hOAT3. When prioritized based on the peak unbound plasma concentrations of these compounds, three inhibitors for hOAT1 and seven inhibitors for hOAT3 were subsequently identified with high inhibitory potency (>95%). Computational analyses revealed that inhibitors and non-inhibitors can be differentiated from each other on the basis of several physico-chemical features, including: number of hydrogen-bond donors, number of rotatable bonds, and topological polar surface area (TPSA) for hOAT1; and molecular weight, number of hydrogen-bond donors and acceptors, TPSA, partition coefficient (Log P7.4), and polarizability for hOAT3. Pharmacophore modeling identified two common structural features associated with inhibitors for hOAT1 and hOAT3, viz., an anionic hydrogen-bond acceptor atom, and an aromatic center separated by ~5.7 Å. Such model provides mechanistic insights for predicting new OAT inhibitors. PMID:22973893